Hexamethylenediamine (HMD) Product Stewardship Summary January 17, 2013
Hexamethylenediamine (HMD) Product Stewardship Summary January 17, 2013
Hexamethylenediamine (HMD) Product Stewardship Summary January 17, 2013
Ascend Performance Materials is a United States based chemical company with global
focus. We are focused more than ever before on our customers to understanding
their unique challenges in the market, to developing product solutions that address
their market needs, and to providing excellent customer and technical service. For
more information on our products please visit www.ascendmaterials.com.
Ascend Performance Materials
600 Travis Street, Suite 300
Houston, TX 77002
1-713-315-5700
Product Stewardship
1-850-968-8411
[email protected]
This document is intended to provide an overview of the major properties, uses, hazards and safe handling practices of this
product. Although the information and recommendations set forth herein (hereinafter "Information") are presented in good
document
2013
Ascend
Performance
Materials
faith This
and believed
to be correct
as of the
date hereof,
Ascend Performance
MaterialsLLC
LLC makes no representations as to
the completeness or accuracy thereof. Information is supplied upon the condition that the persons receiving same will make
their own determination as to its suitability for their purposes prior to use. In no event will Ascend Performance Materials LLC
be responsible for damages of any nature whatsoever resulting from the use of or reliance upon Information. Please consult
the references at the end of this document for more detailed information.
Hexamethylene Diamine
Product Stewardship Summary
______________________________________
Chemical Family:
Chemical Name:
Synonyms:
CAS. Number:
EC Number:
Formula:
Organic di-amine
1,6-Hexanediamine
HMD; Diamine
124-09-4
204-679-6
H2N(CH2)6NH2
H2N
NH2
Introduction
HMD is a high production volume chemical, with more than 2 billion pounds produced annually
worldwide. Ascend Performance Materials LLC is one of the worlds leading producers of HMD.
Ascend produces this material in our Cantonment, FL, USA and Decatur, AL, USA facilities, for
distribution to our customers worldwide. Ascend provides HMD in a variety of package sizes (55 gallon
drums, Totes, Tank Truck, ISO Container, Rail Car and Bulk Ship Compartment), and in several grades
which vary in water content, from anhydrous to 70% HMD.
Use as a monomer:
HMDs largest use is a monomer in formation of various polymers. These include
Nylon 6,6 The reaction product of HMD and Adipic Acid (Such as Ascends Vydyne and
Ascend resins)
Other polymers, such as Nylon copolymers, and Wet Strength Resins for paper manufacture
Properties of HMD
Physical Properties
Commercially, 100% HMD is a white crystalline solid. It is also available as a 70 to 98% water solution.
HMD has a very high thermal expansion coefficient at its melt point. Below its melt point, HMD
molecules are very tightly packed together. When anhydrous HMD melts, the change from the tightly
packed structure to a liquid structure results in a volume increase of about 17%; the reverse of this is
true when HMD freezes.
For this reason, containers of HMD should be vented during heating or cooling. Permanent handling
systems should contain process vents to prevent damage or leakage from an unexpected change in
temperature.
The volume change for HMD solutions is not as dramatic, but is still substantial. Once either anhydrous
or aqueous HMD is above its melt point, volume expansion is more gradual, and is in line with what is
expected for organic fluids.
Chemical Properties
Available chemical information is below. This data is a combination of Ascend historical data, and data
submitted as a part of the joint REACh registration. The REACh data may differ slightly, and is the
result of consensus among many producers of HMD. Differences may be due to crystal properties or
measurement methods.
Parameter
Appearance:
Crystalline Density
pH at 25C:
Ascend Data
White Crystalline Solid
0.8477 g/cm3
Wt% 0.1
1.0
10
pH
11.45 11.94 12.52
Viscosity
Solid at Room Temperature;
1.5 mPa.s @ 50C
Melting Point:
40.87C
HMD Product Stewardship Summary
Boiling Point:
Flash point:
Flammability:
Upper-lower
flammability/ Explosive
limits:
Vapor Pressure:
Relative Density:
Solubilities:
Partition Coefficient:
Autoignition
temperature
Dissociation constant
1000 Pa at 78.5C
815.7 kg/m3 at 80C (Molten)
Water - 637 g/L at 20 C (63.7%)
Log Kow (Pow): 0.04 at 25 C
Log Kow = 0.4 (un-ionized form, pH >
13)
Log D = 3.75 at pH = 7.5
315C
pKa = ca. 10.7
Combustion Properties
Under the 2012 revision of the OSHA Hazcom standard (GHS), HMD is considered as Flammable
Category 4 by OSHA. HMD meets the US Department of Transportation (DOT)s combustible criteria;
however, in the Hazardous Materials Table, DOT has chosen to classify HMD only as a Corrosive
material.1 HMD has a flashpoint of 185F (85C), and if HMD burns in a fire event, it will release water
and carbon dioxide, along with ammonia, nitrogen oxides, carbon monoxide and possibly other low
molecular weight nitrogen containing hazardous materials.
HMD has had a variety of autoignition values measured and published. The value which Ascend
considers the most scientifically valid is 315C at 1027 hPa.2
Carbamate Formation
HMD is a strong base, and will spontaneously react with Carbon Dioxide (a weak acid) in the air. The
reaction product of these two chemicals is hexamethylenediamine carbamate, CAS 143-06-6. Since
HMD is a semi-volatile material, this reaction will take place in the air any time liquid HMD is exposed to
HMD Product Stewardship Summary
March 4, 2013
5
air. It appears as a thin, hazy, white smoke, although it is not smoke at all.
Carbamate will settle out onto surfaces as a fine powder.
Although HMD Carbamate is a safe material (as a neutralized form of HMD), its spontaneous formation
is important for a variety of health and safety reasons. HMD Carbamate can accumulate in tank or
process vents, or any place where HMD may be leaking from a process or storage facility. If process or
storage vents become plugged with HMD Carbamate, the integrity of the process may be challenged,
as over (or under) pressurization can occur in a system with plugged vents. The HMD customer
should have a system of vent inspection and cleaning, along with a preventive maintenance program
which addresses vent issues.
HMD Carbamate can serve an important warning function, as it is an indicator of leaking or venting
HMD. While HMD carbamate is a lower acute hazard than HMD, care should be taken in its removal,
as it is possible for pockets of unreacted HMD to be present within it, and it may be serving as a plug
for a pressurized system.
Figure 1 HMD Carbamate collected on a leaking rail car filling valve, and surrounding surfaces
Figure 2 HMD Carbamate collected on surface of a drum after a nearby spill. HMD Carbamate is the
white haze on the upper portions of the drums.
March 4, 2013
6
HMD is safe as industrial reactant or monomer when handled and used responsibly in the
manner intended.
HMD must be carefully controlled through engineering and protective equipment and safe work
practices combined with personal protective equipment.
Like most caustic materials, HMD is corrosive to the skin, eyes and mucous membranes. If not
quickly and thoroughly removed, permanent damage may occur. Opportunity for these effects
can be minimized through good industrial practice and personal protective equipment.
HMD is biodegradable, and poses no risks to the environment from industrial use.
Value
0.5 ppm
0.5 ppm
0.5 ppm
2.3 mg/m3
0.5 ppm
2.3 mg/m3
0.5 ppm
2.3 mg/m3
1.0 mg/m3
0.5 ppm
2.4 mg/m3
0.5 ppm
0.5 ppm
0.5 ppm
0.5 ppm
2.3 mg/m3
0.5 ppm
1.0 ppm
0.5 ppm
0.5 ppm
2.3 mg/m3
2.3 mg/m3
0.5 ppm
2.3 mg/m3
0.5 ppm
0.5 ppm
2.3 mg/m3
0.5 ppm
0.5 ppm
0.1 mg/m3
Type of Value
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
15 minute STEL
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
March 4, 2013
7
Malaysia: OEL
Norway OEL
Peru OEL
Portugal : OEL
Romania: OEL
Russian Federation: OEL
Serbia and Montenegro: MAC Value
Singapore: PEL
Spain : VLA-ED
United Arab Emirates
United States - OSHA
United States - California
Uruguay
Venezuela CAP
0.5 ppm
2.3 mg/m3
0.5 ppm
1.0 ppm
0.5 ppm
2.4 mg/m3
0.5 ppm
1.0 mg/m3
5.0 mg/m3
0.1 mg/m3
1.0 mg/m3
0.2 ppm
0.5 ppm
2.3 mg/m3
0.5 ppm
2.4 mg/m3
0.5 ppm
2.3 mg/m3
0.5 ppm
0.5 ppm
2.3 mg/m3
0.5 ppm
0.5 ppm
8-hr TWA
8-hr TWA
15 minute STEL
8-hr TWA
8-hr TWA
8-hr TWA
15 minute STEL
Ceiling Limit, Vapor
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
8-hr TWA
March 4, 2013
8
Oral Toxicity HMD is classified under GHS as harmful if swallowed (H302). In animal studies, the
LD50(rat) value for HMD is 1160 mg HMD/kg of body weight. As HMD is a caustic material, it will cause
painful and harmful burns to the mouth and throat. The oral toxicity value is based on a gavage study,
where the substance is placed directly into the stomach. While this information is valuable, the health
effects of permanent burns to the mouth and upper digestive tract, including complete destruction of
tissue, would be seen from any amount of HMD entering the mouth.
Inhalation Toxicity There is no available inhalation toxicity value for HMD. Based on available data,
HMD is classified under GHS as may cause respiratory irritation, H335. This classification is based on
a 13 week inhalation study. The No Observed Adverse Effect Concentration (NOAEC) is 10 mg/m,
with the effects seen including cellular irritation in the nose and larynx. Inhalations of large quantities of
HMD containing mist would likely cause chemical burns to the nasal passages.
Dermal Toxicity HMD is considered as moderately toxic by dermal exposure, and is classified under
GHS as Harmful in contact with skin, Category 4. When HMD was applied to rat skin, the LD50 value
is 1900 mg HMD/kg of body weight. The dose/response curve shows no mortality at 1400 mg/kg, and
completely mortality at 3000 mg/kg.
While this information is valuable for evaluation of whole body toxicity, we wish to stress that any
amount of HMD on the skin will result in painful skin burns. In the dermal study mentioned above,
doses which were fatal to most of the test animals (2000 mg/kg and higher) resulted in skin lesions
which were unable to heal; lower doses resulted in wounds which healed prior to the end of the study,
characterized by scabbing and scarring.
Chronic Effects
In the workplace, chronic effects from HMD exposure may occur via skin, eye and mucus exposure to
the eyes, or inhalation of HMD containing mist.
Sensitization HMD has not been tested for sensitization properties. Since it is a skin corrosive
material, protection from the corrosive effects of HMD should protect against any sensitization concern.
Oral Exposure Many repeat dose feeding studies have been conducted on HMD, by many different
organizations, of varying quality and relevance to risk assessment. Two week animal feeding studies
have shown that ingestion of HMD had a No Observed Adverse Effect Level (NOAEL) of 335
mg/kg/day in male rats, and 390 mg/kg/day in female rats. This was the highest dose tested, which
means that no statistically significant effects were seen.
Inhalation Exposure In a 13 week study of rat exposure to chloride salt of HMD, effects were seen in
the nose and larynx of the tested animals at the higher concentrations tested (31 and 100 mg HMD
salt/m3). The No Observed Adverse Effect Concentration (NOAEC) was judged to be 10 mg HMD
salt/m3. Similar findings were found in mice, also with a NOAEC of 10 mg HMD salt/m3.4 The toxicity
observed for HMD results primarily from the irritant properties of the chemical
Cancer Several studies have shown that HMD does not cause genetic mutations in bacteria or
animal cells. No long term animal cancer studies exist for HMD, as they are considered scientifically
unjustified, due to:
Lack of systemic toxicity at low levels of exposure
Negative results in genetox studies
Corrosive nature of HMD, leading to need for tight industrial controls on its use.
HMD Product Stewardship Summary
March 4, 2013
9
REACh Registration
In 2010, HMD was registered for continued, large scale use in Europe. Ascend was part of the
consortium which helped assemble the registration dossier. This comprehensive review contained
hundreds of studies, and narrowed the available dataset down to the most scientifically valid studies.
The following data was used for regulatory assessment:
Acute Animal Toxicity, Sensitization and Corrosion Data
Exposure Route
Type of Test
Species
Oral
LD50 oral gavage
Sprague-Dawley
rat
Inhalation
Not applicable
Dermal
LD50 occlusive
Sprague-Dawley
rat
Skin irritation
In vitro membrane barrier
in vivo
test method (corrositex
test)
Eye irritation
equivalent or similar to
New Zealand rabbit
92/69/EEC, B.5
Fisher 344/N Rat
Respiratory
subchronic (inhalation:
irritation
aerosol) (whole body)
Value
1160 mg/kg bw (male/female)
Skin
Sensitization
Exposure: 13 weeks (6
hours plus T90 (30
minutes) per day, 5 days
per week)
No reliable information (key study or weight of
evidence) was available for sensitisation
assessment
Repeat dose
Dermal:
Repeat dose
Inhalation:
Species
Fisher 344/N Rat
not sensitising
Value
NOAEL: 335 mg/kg bw/day
Target organs: other: all
gross lesions and masses
NOAEC: 10 mg/m
Target organs: nose, larynx
Exposure: 13 weeks (6
hours plus T90 (30
minutes) per day, 5 days
HMD Product Stewardship Summary
March 4, 2013
10
Mutagenicity In
Vivo
bacterial reverse
mutation assay (e.g.
Ames test) (gene
mutation) (OECD 471)
oral: gavage
chromosome
aberration assay
(chromosome
aberration) (OECD
475)
inhalation: aerosol
Carcinogenicity
Reproductive
and
developmental
toxicity
Developmental
toxicity
(Teratogenicity)
Chinese
hamster
ovary
negative
Salmonella
typhimurium
negative
SpragueDawley Rat
Mouse
micronucleus assay
(chromosome
aberration) (OECD
474)
The substance is classified as corrosive and irritant for respiratory tract. HMD is only
used in industrial area. Hence, there is no evidence or long-term human exposure.
Moreover, studies showed a lack of genotoxicity together with a lack of systemic
toxicity for HMD.
SpragueNOAEL = 500 mg/kg bw/day
Oral, in feed, 2
Dawley Rat
generation
(equivalent to OECD
416)
SpragueNOAEL = 300 mg/kg bw/day
oral: gavage
Dawley Rat
Prenatal
Developmental Toxicity
Study (OECD 414)
March 4, 2013
11
Exposure pattern
DNEL
Workers
Not relevant
n.a.
1.62 mg/m
Qualitative assessment
Acute dermal, local effects
based on corrosivity of HMD
Qualitative assessment
Long-term dermal, systemic effects
based on corrosivity of HMD
Long-term inhalation, systemic effects * Not relevant
Long-term oral, systemic effects
No information available
Qualitative assessment
Long-term dermal, local effects
based on corrosivity of HMD
Long-term inhalation, local effects
0.54 mg/m
* No inhalation study is needed since HMD is classified as corrosive
General population
Exposure unlikely
No peak exposure is
expected
1.2 mg/m
Exposure unlikely
Exposure unlikely
0.56 mg/kg bw/day
Exposure unlikely
0.4 mg/m
Use of this data for Risk Assessment should be performed by qualified risk management professionals.
In addition to basic physical, chemical and toxicological data, REACh registration requires that the
registrant proves the HMD is safe when used properly, in the types of end uses seen within Europe.
Since all major uses of HMD occur in Europe, this health assessment has relevance for the rest of the
world. It was successfully shown that for 6 different types of Exposure patterns, the risk to human
health and the environment was sufficiently controlled, and HMD may continue to be used in current
applications. The typical end uses for HMD were covered, with the exception of food, drug and
cosmetic use; these are not within the scope of REACh. Please see Ascends Extended Safety Data
Sheet for registration details5.
March 4, 2013
12
Biodegradation
HMD has been shown to be readily biodegradable in aerobic and freshwater conditions in the
environment. HMD was shown to be 82% degraded in a GLP compliant study.
Aquatic Toxicity
The acute toxicity of HMD to aquatic organisms has been extensively studied. It has been concluded
that through normal use, disposal and waste treatment, HMD should not adversely affect freshwater or
marine organisms. As with any base, if HMD is placed in a pure water environment, it will raise the pH
of the water. Any organisms which are in the water will be affected by such a pH change. Studies
have shown that a pH change of 3-4 units will be fatal to 50% or more of organisms which are present
in the water.6 Aquatic toxicity data for HMD is shown below.
If a large spill of HMD was to occur, and this spilled material would enter surface water, clearly there
may be acute toxic effects. HMD, when properly controlled and treated, poses no hazard to the aquatic
environment.
Aquatic Toxicity
Exposure Route
Fish, Short Term
Fish, Long Term
Aquatic Invertebrates,
Short Term
Aquatic Invertebrates,
Long Term
Algae and aquatic
plants
Type of Test
Species
LC50, freshwater, static, 96 hr
Pimephales promelas
(OECD 203)
Study waived scientifically unjustified
EC50, freshwater, static, 48 hr
Daphnia magna
(OECD 202)
NOEC, Freshwater, 21 day
Daphnia magna
Value
1825 mg/L
10 mg/L
Pseudokirchnerella
subcapitata (algae)
31.5 mg/L
4.2 mg/L
March 4, 2013
13
Aquatic microorganisms
Pseudomonas putida
12.5 g/L
March 4, 2013
14
References
1
March 4, 2013
15