Hexamethylenediamine (HMD) Product Stewardship Summary January 17, 2013

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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]

Ascend Performance Materials is a member company of the


American Chemistry Council. Ascend is committed to the principles
of Responsible Care and to the proper stewardship of its products.
This document is intended to provide the user with access to health
and safety information on Ascends products. ACC is not responsible
for the content of this document and does not warrant the accuracy of
information posted in this or other similar documents. Information for
the chemical(s) listed has been developed independently by each
company (or in some cases, a group of companies). Each company is
responsible for the content of its own product stewardship summary.
For more information about the content of this document, users
should contact Ascend Performance Materials.
ASCEND PERFORMANCE MATERIALS and the A LOGO are trademarks of Ascend Performance Materials Operations LLC.
These trademarks have been registered in several jurisdictions throughout the world, including the United States and the
European Community, and are the subject of numerous pending applications for registration. Responsible Care is either a
registered trademark or trademark of the American Chemistry Council in the United States and/or other countries.

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.

Conclusion of Safety for Use


HMD is safe for industrial and limited commercial uses, when used with proper care and responsibly.
This includes adherence to Safety Data Sheet and labeling guidance, along with good industrial
hygiene, process safety and waste disposal practices. It is up to the customer to determine fitness for
use in their facility, handling systems, reaction processes and in their reacted or formulated products.

Chemical Inventory Listings


HMD is allowed for commerce in every world area, and is listed on the following Chemical Inventories:
Country/World Area
Listed Name
Other Designation
Australia (AICS)
1,6-Hexanediamine
Canada (DSL)
1,6-Hexanediamine
China (IECSC)
1,6-Hexanediamine
1,6-
European Union
Hexamethylenediamine
(EINECS)
European Union
Hexamethylenediamine
Registered by
(REACh)
Ascend
Japan(ENCS, IHSL)
1,6-Hexanediamine, Hexamethylenediamine
(2)-153
Korea (ESL)
Hexamethylenediamine
KE-18611
New Zealand (NZIoC)
1,6-Hexanediamine
HSR002749
Philippines (PICCS)
1,6-Hexanediamine
Switzerland (ChemO)
Hexamethylendiamin
G-1682
Turkey
Hekzametilen diamin
United States (TSCA)
1,6-Hexanediamine
Please contact Ascend for more information regarding REACh registration and applicability for EU/EEA
customers
HMD Product Stewardship Summary
March 4, 2013
3

Uses for HMD


HMD is used in a variety of ways, to make industrial and consumer products. Typical uses include:

Use as an industrial intermediate:


HMD is reacted with other chemicals to form reactive coating components, scale and corrosion
inhibitors and other chemical products. These include:
HMD Isocyanate Reactive coating additive
1,6-Hexanediol A monomer in the manufacture of polyurethanes and polyesters

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

Use as a formulation ingredient:

HMD salts may be useful as ingredients in oil/gas extraction fluids.

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

REACh Consortium Data


White Crystalline Solid
0.815 at 25C
No Data
0.95 mPa.s at 80C
39.9 C at 1013 hPa
March 4, 2013
4

Boiling Point:

Flash point:
Flammability:
Upper-lower
flammability/ Explosive
limits:

Vapor Pressure:
Relative Density:
Solubilities:

200C @ 760 mmHg with


decomposition
132C @ 90 mmHg
82C @ 10 mmHg
85C (185F) Cleveland open
cup
US-OSHA Flammable Cat. 4
Data Set 1
Data Set 2
Data Set 3
LEL : 0.9
LEL: 0.7%
LEL : 0.9
UEL : 4.1
UEL:6.3%
UEL : 7.6

Completely Miscible with water


at 25C

Partition Coefficient:

Autoignition
temperature
Dissociation constant

201 C at 1013 hPa

85C (185F) Closed Cup


Non flammable by GHS/CLP
No Values Established; Classified as
non-explosive by GHS/CLP

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

Corrosion and Material Properties


Under certain conditions, HMD may be corrosive to steels, and is corrosive to copper and copper
alloys. Copper, Brass and Bronze should never be used for HMD service. Anhydrous and Aqueous
HMD are commonly stored in unlined Carbon Steel storage tanks.
Upon prolonged exposure, HMD can soften, swell and weaken various polymeric materials, such as
natural and synthetic rubber. Proper engineering determinations should be made for designing
pressurized handling systems for HMD, and selecting gasket and sealant materials for HMD service.

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.

With time, HMD

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.

HMD Product Stewardship Summary

March 4, 2013
6

Health Affects Overview


HMD has been extensively studied by manufacturers, governmental agencies and researchers around
the world. Hundreds of studies have been conducted, and these studies have shown that:

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.

Established Occupational Exposure Limits


In many jurisdictions, occupational exposure limits have been established. While many of these are
identical some variance does exist. These are limits above which it is deemed necessary to have
employees protected from inhalation exposure. The current established limits are:
Jurisdiction or Authority
ACGIH TLV:
Argentina OEL
Austria
Bahrain
Belgium: OEL
Bulgaria
Canada: Alberta OEL
Canada: British Columbia OEL
Canada: Manitoba OEL
Canada: Ontario OEL
Canada: Quebec OEL
Canada: Saskatchewan OEL
Columbia OEL
Denmark : OEL
Hungary: AK Value
Iceland: OEL
Indonesia: OEL
Ireland : OEL
Israel
Italy : OEL
Latvia: AERs)
HMD Product Stewardship Summary

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

Details on Health Effects


Acute Effects
In the workplace, acute effects from HMD exposure may occur via skin, eye and mucus exposure to the
eyes, or inhalation of HMD containing mist.
Skin Corrosion HMD is a severe skin corrosive material, and its effects should not be
underestimated. HMD causes caustic burns to the skin, resulting in permanent scarring, pain and
long lasting physical effects. The GHS classification of HMD is Causes severe skin burns and eye
damage, H314.
Caustic materials such as HMD literally dissolve skin. HMD saponifies fats from skin cells and
denatures proteins; the fats become water dispersible, and this effect causes cell walls to break down,
allowing the chemical to penetrate deeper into the skin. This type of damage is known as liquefaction
necrosis. Such action persists until the chemical is neutralized.
If HMD gets on the skin, intense burning will be felt, as skin nerves are affected. The skin area will fell
soapy and slick; this effect is due to the breakdown of the cell walls, and the liberation of water and
fats from the cells. HMD should be immediately and thoroughly removed from the skin. Medical care
should be sought.
Eye Corrosion Similar to skin effects, HMD is a severely corrosive material to the eyes. The
GHS classification of HMD is Causes severe skin burns and eye damage, H314. HMD will cause the
cornea to become cloudy, and affect cell walls of eye cells in the same fashion as skin cells. While
detailed studies of HMD eye effects do not exist, other highly caustic materials (such as sodium
hydroxide) can completely penetrate the eye in 40 seconds3.
HMD Product Stewardship Summary

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)

1900 mg/kg bw (male/female)


corrosive

Highly irritating, induced


irreversible effects
Irritating; STOT SE3
NOAEC: 10 mg/m

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/Chronic Toxicity Data


Exposure Route
Type of Test
Repeat dose
subacute (oral: drinking
Oral:
water)

Repeat dose
Dermal:

Repeat dose
Inhalation:

Exposure: Drinking water


solutions ad libitum on a
continuous basis for 15
days (Continuous basis (ad
libitum)) (OECD 408)
The study is scientifically
unjustified considering
animal welfare since HMD
is classified as corrosive; at
non-irritating
concentrations
subchronic (inhalation:
aerosol) (whole body)

Species
Fisher 344/N Rat

Target organs: nose, larynx

not sensitising

Value
NOAEL: 335 mg/kg bw/day
Target organs: other: all
gross lesions and masses

Fisher 344/N Rat

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

per week) (OECD 413)


Carcinogenicity/ Mutagenicity Data
Mutagenicity In mammalian cell gene
Vitro
mutation assay (gene
mutation) (OECD 476)

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

Genotoxicity: negative (male/female);


toxicity: yes

Mouse

Genotoxicity: negative (male/female);


toxicity: no effects

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)

Specific Target Organ Toxicity (STOT)


HMD was classified as specifically toxic to the respiratory tract. Exposure to HMD mist or vapor may
cause irritation.
The REACh Risk Assessment process requires that Derived No Effect Levels (DNELs) be calculated
for likely exposure routes. These values were derived from the available best data, and by using
ECHAs methodology for risk assessment.

HMD Product Stewardship Summary

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11

Exposure pattern

DNEL
Workers

Acute inhalation, systemic effects *

Not relevant

Acute dermal, systemic effects

Qualitative risk assessment


based on corrosivity of HMD

Acute oral, systemic effects

n.a.

Acute inhalation, local effects

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.

Environmental Affects Overview


HMD has been extensively studied by manufacturers, governmental agencies and researchers around
the world. Hundreds of studies have been conducted, and these studies have shown that:

HMD is not Persistent, Bioaccumulative or Toxic in the environment.


HMD is readily biodegradable in water.
HMD is readily broken down in both aerobic and septic waste disposal systems
While HMD is shows low or moderate toxicity to aquatic in laboratory studies, these are not
reflective of real world conditions. HMD is a strong organic base acid, and raises the pH of
water. These toxic effects seen are negated when the pH of the test medium is adjusted back
to an environmentally relevant level. Further explanation is below.
HMD undergoes photo and chemical degradation.
Ultimate chemical and biodegradation products are carbon dioxide and water.

HMD Product Stewardship Summary

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12

Details on Environmental Effects


HMDs primary uses do not result in substantial releases into the environment. In almost all cases
HMD is an intermediate or monomer, used within a chemical facility, and converted to another chemical
substance. Proper use and disposal practices will minimize releases to the environment from all uses
of HMD.

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.

Wastewater Treatment Facilities


No specific wastewater treatment data exists for HMD. Based on the readily biodegradable status of
HMD, no negative effects on wastewater treatment processes are expected from normal use and
disposal.

REACh Dossier for HMD Environmental Health Effects


In 2010, HMD was registered for continued, large scale use in Europe. Ascend was part of the
consortium which helped assemble the registration dossier. 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. In preparation of the dossier for HMDs
REACh registration, all available data (through June 2010) was reviewed7. 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:

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

NOEC, Freshwater, static, 72 hour

10 mg/L

HMD Product Stewardship Summary

Pseudokirchnerella
subcapitata (algae)

31.5 mg/L
4.2 mg/L

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Aquatic microorganisms

EC10, freshwater, static, 20 hr

Pseudomonas putida

12.5 g/L

Persistence and degradability


Biodegradation
Hexamethylene was found to be readily biodegradable meeting the 10-day
window in a OECD 301D closed bottle test (van Ginkel, 2009).
Bioaccumulative potential
Based on its Log Kow < 3.0 the substance is not believed to bioaccumulate, moreover, due to the ready
biodegradability of the substance with discharge only via STP, exposure via the aquatic environment is
expected to be low.
Mobility in soil
Based on readily biodegradability and to very low Log Kow, the substance is not expected to adsorb.
Results of PBT and vPvB assessment
The screening assessment of the available data for Hexamethylene diamine indicates that the data
show that the properties of the substance do not meet the specific criteria detailed in Annex XIII, i.e. it is
not P/vP, not B/vB, and not T.
Thus, the Hexamethylene diamine is not considered a PBT/vPvB.
The REACh Risk Assessment process requires that Predicted No Effect Concentrations (PNECs) be
calculated for likely exposure routes. These values were derived from the available best data, and by
using ECHAs methodology for risk assessment.
Exposure pattern
PNEC
PNEC aqua (freshwater)
0.42 mg/L
PNEC aqua (marine water)
0.04 mg/L
PNEC aqua (intermittent releases)
0.32 mg/L
Freshwater Sediment
1.44 mg/kg sediment dw
Marine Sediment
0.144 mg/kg sediment dw
Soil
0.0541 mg/kg soil dw
PNEC STP
12.5 g/L
PNEC (oral, secondary poisoning)
Irrelevant
Use of this data for Risk Assessment should be performed by qualified risk management professionals.

REACh Exposure Scenarios and Proof of Safe Use


Within REACh, once the PNECs are calculated, a registrant must prove that the uses of the substance
result in exposures which are less than the PNEC. In 6 different exposure scenarios, using data
provided by downstream users, safe use was proven for each condition. The typical REACh regulated
end uses for HMD were covered; please see Ascends Extended Safety Data Sheet for details8.

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GHS Classification and Labeling


Under the Global Harmonized Standard for Hazard Communication (GHS), Version 4, Adipic Acid is
classified as follows:
Category
Sub-Category
Classification
Physical Hazards
Flammable Liquids
Category 4, Combustible Liquid
Acute Health Hazards
Serious Eye Irritation/
Category 1, Causes Serious Eye Damage
Eye Damage
Skin Corrosion/Irritation Category 1B, Causes sever skin burns and eye
damage
Acute Toxicity Oral
Category 4, Harmful if swallowed
Acute Toxicity - Dermal
Category 4, Harmful in contact with skin
Chronic Health Hazards
Not classified for any Chronic Health hazard
Specific Target Organ
Respiratory Tract
Category 3, May Cause Respiratory Irritation
Toxicity (STOT), Acute
Irritation
Exposure
Acute Environmental
Toxicity to Algae,
Category 3, Harmful to Aquatic Life
Hazards
Invertebrates
Long-term Environmental
Not classified for any long term environmental
Hazards
hazard
Signal Word
Danger
Pictogram

References
1

49CFR 172.101, accessed May 4, 2012


Vibert, Martine, Determination of the flash point, explosion properties and, the auto-ignition
temperature of hexamethylene diamine, Rhodia CRTL, 2007. Unpublished study, summarized in the
REACh registration for HMD
3
Spler & al., Dynamic analysis of chemical eye burns using OCT-HR, J of Biomedical Optics, 2007,12
(4), 041203
4
Hebert, 1993, NTP Technical Report on Toxicity Studies of 1,6-Hexanediamine Dihydrochloride (CAS
No. 6055-52-3). http://ntp.niehs.nih.gov/ntp/htdocs/st_rpts/tox024.pdf (Accessed on July 16, 2012)
5
Ascend Performance Materials e-SDS, 2011
6
S.E. Belanger and D.S. Cherry, Journal of Crustacean Biology, Vol. 10, No. 2 (May, 1990), pp. 225235
7
Ascend Performance Materials, REACh Dossier for CAS 5064-31-3, November 2010.
8
Ascend Performance Materials e-SDS, 2011
2

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