ETHANOLAMINES

Product Information
 Ethanolamines

Table of Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . .2

Sales Specifications . . . . . . . . . . . . . . . . . . . . . . .3

Analytical Procedures . . . . . . . . . . . . . . . . . . . . . .5

Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6

Physical Properties . . . . . . . . . . . . . . . . . . . . . . . .9

Chemical Properties . . . . . . . . . . . . . . . . . . . . . .22

Handling & Storage . . . . . . . . . . . . . . . . . . . . . .31

Health & Safety . . . . . . . . . . . . . . . . . . . . . . . . .34

Shipping Information . . . . . . . . . . . . . . . . . . . . .43

Huntsman Sales Offices . . . . . . . . . . . . . . . . . . .44

1
 Introduction
Monoethanolamine, diethanolamine, and triethanolamine
are amino alcohols which were introduced industrially in
this country about 1928 and have been finding applica-
tion in increasing quantities in diverse fields ever since.
Commercial production of ethanolamines is accom-
plished by reacting ethylene oxide with ammonia to
yield a mixture of the three compounds.
By subjecting this mixture to a series of separations,
monoethanolamine, diethanolamine, and tri-
ethanolamine are obtained.
Triethanolamine is offered commercially in two concen-
trations, 85 wt. % and 99 wt. %. The 85 wt. % material
contains up to 15 wt. % diethanolamine.
Physically, these compounds are clear, viscous liquids at
room temperature and white crystalline solids when frozen.
Diethanolamine has the highest freezing point of the group,
28.0°C, and monoethanolamine the lowest, 10.5°C.
2
They all have comparatively high boiling points,
although at elevated temperatures they are subject to
decomposition, particularly diethanolamine.
Their odors are ammoniacal to varying degrees, with
monoethanolamine being the most marked. The
ethanolamines are hygroscopic and miscible with water,
most alcohols, and polyols.
They and their aqueous solutions are alkaline.
Being bifunctional, ethanolamines react with acids to
form esters or salts, and most of their industrial applica-
tions are dependent to some degree on these features.
We have prepared this technical brochure to bring you
the latest available data on ethanolamines in the hope
that it will enable you to use them to optimum advan-
tage in your present operations and to help further your
search for new applications.
 Sales Specifications

The following sales specifications are for the commercial grade for applications requiring guaranteed low levels
products and are subject to change without notice. of chloride and iron. Abbreviated analytical procedures
Special grades are available for unique requirements. for these specifications may be found on page 5 of
Monoethanolamine-LCI, for example, is a high-purity this brochure.

Monoethanolamine Method of Determination

Composition, wt. % ST-35.128

Monoethanolamine 99.5 min.
Diethanolamine 0.1 max.
Triethanolamine –
Color, Pt-Co (APHA) 15 max. ST-30.12
Water, wt. % 0.3 max. ST-31.53, Procedure 6

Monoethanolamine-LCI

Composition, wt. % ST-35.128

Monoethanolamine 99.5 min.
Diethanolamine 0.1 max.
Triethanolamine –
Chlorides as Cl, ppm 1 max. ST-5.50
Color, Pt-Co (APHA) 15 max. ST-30.12
Iron, ppm 0.5 max. ST-37.1
Sulphates, ppm 5.0 max. ST-5.49
Water, wt. % 0.3 max. ST-31.53, Procedure 6

Diethanolamine

Composition, wt. % ST-35.99

Diethanolamine 99.0 min.
Monoethanolamine 0.5 max.
Triethanolamine 0.5 max.
Color, Pt-Co (APHA) 15 max. ST-30.12
Equivalent weight 104.0 min. ST-5.5
106.0 max.
Water, wt. % 0.15 max. ST-31.53, Procedure 6

The above products are clear and substantially free of suspended matter.

3
 Sales Specifications Continued

Triethanolamine 85% Grade 99% Grade Method of Determination

Composition, wt. % ST-35.99

Triethanolamine 85.0 min. 99.0 min.
Diethanolamine 15.0 max. 0.4 max.
Monoethanolamine 0.5 max. –
Color, Pt-Co (APHA) 40 max. 40 max. ST-30.12
Equivalent weight 140.0 min. 148.0 min. ST-5.5
144.0 max. 150.0 max.
Iron, ppm – 10 max. ST-37.1
Water, wt. % 0.2 max. 0.2 max. ST-31.53, Procedure 5

The above products are clear and substantially free of suspended matter.

4

Abbreviated forms of our standard methods of analysis
for use with the ethanolamines specifications are pre-
sented here.
Copies of the methods in detail are available upon
request from our Technical Services team in The
Woodlands, Texas.
CHLORIDES
(Method No. ST-5.50) — A sample of
monoethanolamine-LCI is neutralized to litmus with
nitric acid, a solution of silver nitrate is added, and the
chloride content determined visually by comparison to a
standard.
COMPOSITION
Monoethanolamine product is determined by Method
No. ST-35.128, while diethanolamine product and tri-
ethanolamine product are each determined by Method
No. ST-35.99. Both of these tests use gas chromatog-
raphy.
COLOR
(Method No. ST-30.12) — Color in the three
ethanolamines is determined visually in a 40-ml tube
with an APHA color disc standard or in a 100ml tall-
form Nessler tube with liquid platinum cobalt (APHA)
standards.
Analytical Procedures
EQUIVALENT WEIGHT
(Method No. ST-5.5) — Equivalent weight of
diethanolamine and triethanolamine is determined by
titrating a solution of the ethanolamine with standard
hydrochloric acid using methyl purple indicator.
IRON
(Method No. ST-37.1) Iron in triethanolamine is deter-
mined by atomic absorption spectrophotometry.
SULPHATES
(Method No. ST-5.49) — A sample of
monoethanolamine-LCI is ashed, then dissolved in
hydrochloric acid. The resulting solution is treated with
barium chloride and the turbidity of the sample com-
pared to that of a standard.
WATER
(Method No. ST-31.53) — Water in the three
ethanolamines is determined by the Karl Fischer
method, the end point being detected electrometrically.
Interference by monoethanolamine and diethanolamine
is prevented by the use of glacial acetic acid.
5
 Applications
DETERGENTS
Household and Industrial
The surface-active properties of ethanolamine-fatty acid
soaps find wide use in detergents and emulsifiers.
These soaps are soluble in water and in hydrocarbon
solvents. In hard water, monoethanolamine soaps have
superior lathering properties compared with other
ethanolamine soaps.
Three classes of monoethanolamine derivatives are
used as emulsifiers:
1) Sodium salts of sulfated fatty acid
monoethanolamides
2) alkyl aryl monoethanolammonium sulfonates and
monoethanolamine salts of alkyl sulfuric acid
3) monoethanolamides of fatty acids themselves
All three classes have detergent applications.
Diethanolamine fatty acid concentrates are used as
foam stabilizers in the liquid detergent industry. The most
common triethanolamine soaps are the oleate and
stearate. Emulsification requirements for a stable, well-
dispersed, oil-in-water emulsion are on the order of 2 to
5% triethanolamine saponified with an equivalent
amount of oleic or stearic acid. Oleate soap is water
soluble in all proportions. Solutions of this soap have
very good detergent properties and are widely used with
organic solvents. Triethanolamine soaps are of value in
dry cleaning solvents. Triethanolamine is also used in
making detergent salts of alkyl aryl sulfonic acids.
6
TEXTILES
All three ethanolamines find valuable use in textile
applications for preparing, dyeing, and finishing fibers
and fabrics.
Surface-active agents made from monoethanolamine
are used in the acid bath in the spinning of viscose yarn
to prevent clogging of the spinnerets. Sulfated and sul-
fonated amides are used to mercerize and desize cot-
ton, and to carbonize wool. Ethanolamine soaps of fatty
acids are used in cleaning and scouring textiles and,
with chlorinated solvents, as wetting out agents.
Fatty acid amides of diethanolamine have many uses
(including scouring, rewetting, and softening) and give a
better hand than that obtained with alkyl aryl sulfonates
and nonionics.
The triethanolamine soap of oleic acid is used as an
emulsifying agent in textile lubricants. Characterized by
their excellent emulsifiability and ease of removal,
ethanolamine-based knitting oils prevent gum from
clogging needles and decrease static buildup on the
fiber during processing.
Triethanolamine acts as a temporary gas fading
inhibitor for protecting yard goods stored over an
extended period.
Combined with sulfamic acid, ethanolamines are used
as fire-retardant coatings for fabrics.
GAS TREATING
Monoethanolamine and diethanolamine are both widely
used for the absorption of acid gases such as hydrogen
sulfide and carbon dioxide. A cyclic process is
employed involving contact with an aqueous solution of
the ethanol-amine and subsequent stripping of the acid
gas from solution.
Monoethanolamine is the preferred absorbent for purifying
natural gas. For refinery streams containing carbonyl sul-
fide, diethanolamine is preferred, since monoethanolamine
reacts with carbonyl sulfide to form stable compounds
from which the amine may not be recovered.
Hydrogen sulfide stripped from amine solutions may be
further processed to elemental sulfur. Recovery of carbon
dioxide from flue gas with ethanolamine accounts for a
large portion of carbon dioxide marketed. In the manu-
facture of ammonia, methanol, or hydrogen by certain
processes, it is necessary to remove carbon dioxide from
the synthesis gas streams. This is frequently done by the
same ethanolamine contact process.
AGRICULTURE
The excellent emulsifiability of the “soluble” oils made
from ethanolamine soaps has led to their wide use in
insecticides and herbicides.
SHAMPOOS & PERSONAL CARE
APPLICATIONS
Ethanolamine soaps are frequently used in hand
lotions, cosmetic creams, cleansing creams, shaving
creams, shampoos, waterless and industrial hand
cleaners, and medicated soaps. Mono- and
diethanolamine are used to prepare fatty acid amides
which are included in minor amounts in the formula-
tions as thickening agents. High-purity monoeth-
anolamine-LCI guarantees low levels of chloride and
iron in these applications. In shampoos, the
diethanolamides have the added advantage of stabilizing
the foam of the principal surfactant. Triethanola-mine, on
the other hand, is used to make the lauryl sulfate salt
which is the major active ingredient in some liquid
shampoos.
For cosmetic applications, triethanolamine soaps, of
which the triethanolamine stearate is the most popular,
are used as emulsifying agents. The emulsions pro-
duce creams of desirable texture and allow the cos-
metic to be removed by simply washing with water.
WAXES, POLISHES & COATINGS
Ethanolamine soaps are employed as emulsifying and
dispersing agents for many types of waxes and polish-
es. These polishes are used on floors, wood, glass,
ceramic ware, automobiles, shoes, and furniture. The
detergent property of these water-emulsion waxes
also helps in cleaning the surface being polished.
Ethanolamines are also employed in various coatings
such as resins, lacquers, and paints. Combined with
mineral oils, ethanolamine soaps are used in preparing
emulsion paints. A varnish resin is made with tri-
ethanolamine, phthalic anhydride, and oil.
Monoethanolamine and resin yield a product used to
disperse paint pigment. Triethanolamine aids in the
dispersion of shellac, dyes, rubber latex, and casein,
and in the neutralization of acidic clays, oils, and pig-
ments. The ethanolamines are also used in paint and
varnish removers, and paint and wall cleaners.
7
 Applications Continued
CEMENT ADDITIVES
Triethanolamine salts of various acids are used as
cement and concrete additives to reduce setting time
and increase resistance to crumbling due to repeated
freezing and thawing.
LUBRICANTS & METALWORKING
COMPOUNDS
The addition of ethanolamine soaps to mineral oils pro-
duces a “soluble” oil used in greases, cutting and lubri-
cating oils, petroleum-water demulsifiers, and oil emulsi-
fiers. When incorporated in sulfurized hydrocarbon oils,
the ethanolamines act as odor inhibitors. Diethanolamine
is employed to make the sulfurized oils used in extreme-
pressure lubricants.
Ethanolamines are also used in additives which lower the
pour point of lubricating oils. One such additive, made
with triethanolamine and aluminum stearate, tends to
lower the pour point without requiring the removal of
paraffin wax.
Triethanolamine is also used as an emulsifying agent
in grinding compounds to prevent loading of the
grinding wheel.
8
MISCELLANEOUS
Monoethanolamine and triethanolamine are used in resin
preparation. The rubber industry reacts monoethanol-
amine with carbon disulfide to make 2-mercaptothiazo-
line, which accelerates the vulcanizing of rubber.
Diethanolamine and triethanolamine are employed in con-
trolling the pH of latex emulsions and in neutralizing acid
clays used in rubber compounding.
Electronics grade monoethanolamine is used as a com-
ponent of photoresist strippers. These strippers are used
to remove photoresist after etching or plating. Strippers
are used in both the PWB and semiconductor segments
of the industry.
Triethanolamine is used as an inhibitor in butadiene plants
employing furfural extraction processes. In the oil fields,
triethanolamine is incorporated into a surface-active
agent used to break petroleum oil emulsions. Additional
uses of the ethanolamines are as solvents, as com-
pounds of soldering fluxes, and in printing inks. They also
find use as intermediates in the production of certain
synthetic resins, in copper-electroplating processes, and
in cleaning compounds used to remove carbon from
aluminum pistons used in internal combustion engines.
The very marked hygroscopicity of the ethanolamines
(particularly monoethanolamine) and their excellent com-
patibility with solvents and other materials has led to their
wide acceptance as plasticizing agents, conditioning
agents, and humectants in many different applications.
 Physical Properties

The following physical properties are for the pure compounds.

Monoethanolamine Diethanolamine Triethanolamine

Boiling point, 760 mm Hg, °C 170.5 269* 360

Flash point, PMCC, °C 95 154 201
°F 204 310 395
Melting point, °C 10.5 28.0 21.2
°F 50.9 82.4 70.2
Molecular weight 61.08 105.14 149.19
Refractive index, nD 1.4539 (20°C) 1.4747 (30°C) 1.4852 (20°C)
Solubility in water, 20°C Complete 95.4 wt. % Complete
Specific gravity 1.0179 (20/20°C) 1.0919 (30/20°C) 1.1258 (20/20°C)
Vapor pressure, 20°C, mm Hg 0.23 <0.01 <0.01
Viscosity, cp 24.1 (20°C) 350 (30°C) 1013 (20°C)
Weight, kg/l 1.02 (20°C) 1.09 (30°C) 1.12 (20°C)
Ib/gal 8.47 (20°C) 9.09 (30°C) 9.37 (20°C)
pH 11.8 11.5 11.0

*Decomposes

9
 Physical Properties Continued

Additional physical properties pertinent to handling
and using the ethanolamines are presented on the
following pages. In most cases, the properties have
been determined in the laboratory using chemically
pure compounds.
An attempt has been made to correlate values which
appear in the literature.
In the case of heats of vaporization, values presented
were calculated from vapor pressure data.

Figure 1
Vapor Pressure Versus Temperature for
Monoethanolamine, Diethanolamine, and Triethanolamine

1,000.0

800.0 Monoethanolamine
600.0 Diethanolamine
500.0 Triethanolamine
400.0

300.0

200.0

100.0

80.0
VAPOR PRESSURE, mm Hg

60.0
50.0
40.0

30.0

20.0

10.0

8.0

6.0
5.0
4.0

3.0

2.0

1.0
30 40 50 60 70 80 90 100 120 140 160 180 220 260 300 340 380
TEMPERATURE, °C

10
 Figure 2
Monoethanolamine Partial Pressure Versus Temperature for Aqueous Solutions

10.0
8.0
50 wt. % MEA
6.0 40 wt. % MEA
5.0 30 wt. % MEA
4.0 20 wt. % MEA
3.0 15 wt. % MEA
10 wt. % MEA
2.0 5 wt. % MEA

1.0
0.80
0.60
0.50
0.40
0.30
PARTIAL PRESSURE, mm Hg

0.20

0.10
0.08
0.06
0.05
0.04
0.03

0.02

0.01
0.008
0.006
0.005
0.004
0.003

0.002

Data courtesy The Girdler Co.

0.001
5 10 20 30 40 50 60 70 80 90 100 110 120 130 140 145
TEMPERATURE, °C

11
 Physical Properties Continued

Figure 3
Diethanolamine Partial Pressure Versus Temperature for Aqueous Solutions

0.10
0.09
0.08
0.07 50 wt. % DEA
0.06 40 wt. % DEA
0.05 30 wt. % DEA
20 wt. % DEA
0.04 10 wt. % DEA
0.03

0.02

0.01
0.009
0.008
0.007
PARTIAL PRESSURE, mm Hg

0.006
0.005
0.004

0.003

0.002

0.001
0.0009
0.0008
0.0007
0.0006
0.0005
0.0004

0.0003

0.0002

Data courtesy The Girdler Co.

0.0001
30 40 50 60 70 80 90 100 110
TEMPERATURE, °C

12
 Figure 4
Boiling Points and Condensation Temperatures of
Aqueous Solutions of Monoethanolamine at 760 mm Hg

Dew point
170
Boiling point

160

150
TEMPERATURE, °C

140

130

120

110

100
0 10 20 30 40 50 60 70 80 90 100
MONOETHANOLAMINE, wt. %

Figure 5
Boiling Points of Aqueous Solutions of Diethanolamine at 760 mm Hg

Diethanolamine may
250
decompose at tem-
peratures above 200 °C
TEMPERATURE, °C

200

150

100
0 10 20 30 40 50 60 70 80 90 100
DIETHANOLAMINE, wt. %

13
 Physical Properties Continued

Figure 6
Freezing Point Versus Composition for Aqueous Solutions of
Monoethanolamine, Diethanolamine, and Triethanolamine

30
20
10
TEMPERATURE, ºC

-10

-20

-30

-40

-50 Triethanolamine
Diethanolamine
-60 Monoethanolamine
-70
0 10 20 30 40 50 60 70 80 90 100
ETHANOLAMINE, wt. %

Table I
Low Freeze Grade Ethanolamine Blends (Composition, Wt. %)

Approx. Freeze Point

Monoethanolamine Diethanolamine Triethanolamine Water °C °F

Monoethanolamine 99.5 min 0.1 max — 0.3 max 11 51

MEA LFG 85% 83-87 .09 max — 13-17 -10 14
Diethanolamine 0.5 max 99.0 min 0.5 max 0.15 max 28 82
DEA LFG 85% — 83-87 — 13-17 0 32
Triethanolamine 85% 0.5 max 15.0 max 85.0 min 0.2 max 18 64
TEA 85 LFG 85% 0.4 max 13.0 max 70.5 min 13-17 -9 16
Triethanolamine 99% — 0.4 max 99.0 min 0.2 max 21 70
TEA 99 LFG 85% — 0.35 max 83-87 13-17 -5 23

14
 Figure 7
Latent Heats of Vaporization Versus Temperature for
Monoethanolamine, Diethanolamine, and Triethanolamine

400
LATENT HEAT OF VAPORIZATION, Btu/lb

360

320

280

240

Monoethanolamine
200
Diethanolamine
Triethanolamine
160
180 220 260 300 340 380 420 460 500 540 580

TEMPERATURE, °F

Figure 8
Surface Tension Versus Temperature for Monoehtanolamine

49
SURFACE TENSION, dynes/cm

48

47

46

45

44

43
15 30 45 60 75
TEMPERATURE, °C

15
 Physical Properties Continued

Figure 9
Surface Tension Versus Composition for Aqueous Solutions of
Monoethanolamine, Diethanolamine, and Triethanolamine at 20°C

74

70
SURFACE TENSION, dynes/cm

66

62

58

54

50 Monoethanolamine
Diethanolamine
Triethanolamine
46
0 10 20 30 40 50 60 70 80 90 100
ETHANOLAMINE, wt. %

16
 Figure 10
Specific Gravity Versus Temperature for
Monoethanolamine, Diethanolamine, and Triethanolamine

1.15

1.10
SPECIFIC GRAVITY, t/68°F

1.05

1.00

0.95

Triethanolamine
Diethanolamine
Monoethanolamine
0.90
50 100 150 200 250 300

TEMPERATURE, °F

17
 Physical Properties Continued

Figure 11
Specific Gravity Versus Composition for
Aqueous Ethanolamine Solutions at 20°C

1.14 9.50

1.13 Triethanolamine
Diethanolamine
1.12 Monoethanolamine
1.11 9.25
SPECIFIC GRAVITY, 20/20°C

1.10

1.09

WEIGHT, lb/gal
1.08 9.00
1.07

1.06 Solutions containing more

than 96% DEA will freeze at
1.05 8.75
20°C
1.04

1.03

1.02 8.50

1.01

1.00
0 10 20 30 40 50 60 70 80 90 100

ETHANOLAMINE, wt. %

18
 Figure 12
Viscosity Versus Temperature for
Aqueous Solutions of Monoethanolamine

100
90
80
70
60
50
40

30

20

10
9
8
7
6
5
VISCOSITY, cp

1
.09
.08
.07
0.6
0.5
0.4

0.3

Monoethanolamine
0.2
50 wt. % solution
20 wt. % solution
Water
0.1
-80 -60 -40 -20 0 20 40 60 80 100 120 140 160 180 200
TEMPERATURE, °C

19
 Physical Properties Continued

Figure 13
Viscosity Versus Temperature for
Aqueous Solutions of Diethanolamine

1,000
800
600

400

200

100
80
60

40

20
VISCOSITY, cp

10
8
6

1
0.8
0.6

0.4
Diethanolamine
50 wt. % solution
0.2
20 wt. % solution
Water
0.1
ñ50 0 50 100 150 200 250 300
TEMPERATURE, °C

20
 Figure 14
Viscosity Versus Temperature for
Aqueous Solutions of Triethanolamine

1,000
800
600

400

200

100
80
60

40

20
VISCOSITY, cp

10
8
6

1
0.8
0.6

0.4
Triethanolamine
50 wt. % solution
0.2
20 wt. % solution
Water
0.1
ñ50 0 50 100 150 200 250
TEMPERATURE, °C

21
 Chemical Properties

Each of the three ethanolamines is characterized by the In aqueous solution:

presence of a basic nitrogen atom and at least one
hydroxyl group and is thus capable of undergoing reac-
tions typical of both amines and alcohols. Whenever it
is possible for a reaction to occur at either the amine or
hydroxyl group, the amine group usually exhibits the In anhydrous solution:
greater activity.

Mono-, di-, and triethanolamine are primary, secondary,

and tertiary amines, respectively; they display the usual
properties of these three classes of nitrogen bases.
Monoethanolamine and diethanolamine undergo a num-
ber of interesting reactions leading to the formation of
various nitrogen heterocycles.
All three of the ethanolamines readily form salts with
inorganic and organic acids.
REACTIONS WITH ACID GASES
The ability of the ethanolamines and their aqueous solu-
tions to absorb carbon dioxide and hydrogen sulfide at
lower temperatures and release these acidic gases at
higher temperatures forms the basis of processes for
the separation of carbon dioxide and hydrogen sulfide
from gas streams.
The absorption of carbon dioxide in the presence of
water leads to the formation of amine carbonates; while
in the absence of water, carbamates result from
monoethanolamine and diethanolamine.
Triethanolamine is effective only in the presence of
water since tertiary amines cannot form carbamates.
SALT FORMATION
The preparation of ethanolamine salts of organic acids
is of principal value in neutralizing or solubilizing these
acids to obtain solutions or emulsions of increased
water solubility or surface activity. In particular, salts of
triethanolamine with fatty acids (e.g., stearic and oleic)
are important as emulsifying agents and special soaps.
Some salts of inorganic acids are useful as soldering
fluxes.
REACTIONS WITH METALLIC SALTS
The three ethanolamines form coordination complexes
with a variety of metallic salts in aqueous or alcoholic
solutions. The colors and melting points of the com-
plexes formed have been used primarily to characterize
the various ethanolamines.
One complex salt may prove to be of more than pass-
ing interest. Monoethanolamine hydrochloride has been
reported to be one of the best solvents for cuprous
chloride (150 g/100 g of solvent).

22
The resulting solution is useful for carrying out reactions Reaction of diethanolamine with an acid or ester yields
with acetylene at high catalyst concentration. several products in addition to the diethanolamides. The
possible products of reaction are indicated as follows:
Solutions of cuprous chloride in monoethanolamine
have been used as catalysts for the preparation of
lewisite (from acetylene and arsenic trichloride) as well
as vinyl halides and vinyl acetylene.

REACTIONS WITH ACIDS, ACID

ANHYDRIDES, ACID CHLORIDES,
AND ESTERS

Monoethanolamine and diethanolamine will react with

acids, acid anhydrides, acid chlorides, or esters to form
ethanolamides.

For example, with acids the first product is an

ethanolamine salt.

The salt is subsequently dehydrated to form the amide

by heating above 180°C.

At even higher temperatures, oxazolines may be pre-

pared.

23
 Chemical Properties Continued
Principal products are the amide, amine ester, and
amide ester.
The reaction of one mole of fatty acid with two moles of
diethanolamine at 140 to 160°C gives a product having
the following approximate composition: 60 to 70%
diethanolamide, 25 to 30% diethanolamine, 3% ester,
and 3 to 5% free fatty acid.
The ester is mainly an ester amine with some ester
amide. In addition, some piperazinediethanol and other
cyclic compounds are formed.
The reaction of one mole of diethanolamine with one
mole of the methyl ester of a fatty acid gives a product
which contains 90% or more of the amide.
The same by-products formed in the previous reaction
are present, although to a much lesser degree. The
amount of unreacted diethanolamine is obviously also
much less.
Sulfonates of the ethanolamides of fatty acids are useful
in the preparation of detergents.
Phthalic anhydride readily gives high yields of β-hydroxy-
ethyl phthalimide when heated at 210°C for 30 minutes
with monoethanolamine.
24
Esters are easily converted to amides by heating with
monoethanolamine, particularly when the alcohol pro-
duced by the reaction is removed by distillation.
Esters of triethanolamine are readily prepared from acid
chlorides or anhydrides in pyridine solution.
Monoethanolamine and diethanolamine usually yield
ester-amides under these conditions.
Esters of triethanolamine can be prepared simply by
distilling water from mixtures of the amine and acids.
The diacetyl derivative of monoethanolamine is avail-
able through use of ketene, acetyl chloride, or acetic
anhydride.
By partial hydrolysis of alkaline solution, the ester link-
age can be saponified without hydrolysis of the amide.
Products reported to be esters of ethanolamines have
been prepared from acid chlorides and ethanolamine
hydrochlorides at 70°C.
Amide formation appears to have been largely avoided.
The reaction is rather violent as hydrogen chloride is
expelled.
N-stearoyl monoethanolamine and O-stearoyl
monoethanolamine can be readily interconverted. Thus
the amide is changed to the ester in 93% yield by an
equimolar amount of thionyl chloride — whereas, the
ester is reportedly transformed into the amide in cold,
slightly alkaline solution.
Monoethanolamine hydrochloride reacts more smoothly
than the free base.
The tris-(β-chloroethyl) amine exhibits ab strong vesicant
action resembling that of other “nitrogen mustards”.

The primary and secondary analogues have no such

action. The chloroethyl amines are most stable as
their hydrochlorides. They are rapidly decomposed in
Condensation of dibasic acids with monoethanolamine alkaline solutions.
and diethanolamine leads to polyester-polyamide resins.
With triethanolamine, cross-linked polyester resins result. REACTIONS WITH CYCLIC
CARBONATES
A number of esters have been prepared from inorganic
acids and the ethanolamines. Some of the nitrates are Both monoethanolamine and diethanolamine form car-
powerful explosives. bamates readily. Thus from ethylene carbonate, N-β-
hydroxyethyl, β-hydroxyethyl carbamate is obtained in
Sulfuric acid esters of monoethanolamine and excellent yield below 50°C.
diethanolamine are intermediates in the preparation of
ethylenimine and morpholine, respectively. β-aminoethyl
sulfuric acid (NH2CH2CH2OSO2OH) is an irregular
ampholyte. It has many properties of the familiar amino
acids and possesses an ester linkage which is very resist-
ant to hydrolysis, probably due to inner salt formation.

This sulfate ester is prepared in high yield by the distilla-

tion of water from aqueous mixtures of mono-
ethanolamine and sulfuric acid.

Replacement of the β-hydroxyl groups in all three Propylene carbonate reacts similarly to give the corre-
ethanolamines is easily accomplished by thionyl chloride. sponding hydroxypropyl carbamate.

25
 Chemical Properties Continued

Certain hydroxy-, halogen-, nitro-, or alkoxy-substituted

aromatic compounds, in which the substituents men-
ALDIMINE AND KETIMINE FORMATION tioned are in activated positions on the aromatic nucle-
us, will give good yields of N-β-hydroxyethylaniline
In reactions characteristic of primary and secondary derivatives when refluxed with monoethanolamine or
amines, monoethanolamine and diethanolamine react diethanolamine. Sodium carbonate is usually added to
readily at moderate temperatures with aldehydes and facilitate the reaction.
ketones to yield aldimines and ketimines. The imines
may be reduced in good yield to the N-alkyl-
ethanolamines. Hydrogenation over platinum oxide or
the Leuckart-Wallach reaction with formic acid gives
particularly good yields.

Under somewhat more vigorous conditions, the inter-

mediate Schiff’s bases can frequently be converted to
oxazolidines.

PREPARATION OF N-SUBSTITUTED Certain nitro compounds may undergo reduction to

ETHANOLAMINES amines under similar conditions.

Monoethanolamine and diethanolamine may be conve- EPOXIDES

niently transformed to the corresponding N-substituted
ethanolamines by the action of a variety of reactive
halogen derivatives (or dialkyl sulfates) in the presence
of alkalies. Thus alkylation will occur with such com-
pounds as benzyl chloride, chloroacetophenone, methyl
iodide, or diethyl sulfate.
Epoxides react rapidly with monoethanolamine and
diethanolamine at ordinary temperatures. This is best
illustrated by the familiar stepwise reactions which occur
during synthesis of the ethanolamines.

For example, complete methylation of

monoethanolamine in virtually quantitative yield to the
quaternary halide leads to the preparation of the quater-
nary base, choline.
Other epoxides (e.g., propylene oxide and cyclohexene
oxide) also provide good yields of the higher substituted
ethanolamines.

26

Excess ethylene oxide can react further with the hydroxyl
groups of triethanolamine to give polyoxyethylene deriv-
atives. Stoichiometric amounts of ethylene oxide and tri-
ethanolamine yield the strong base, tetraethanolammo-
nium hydroxide. The latter, when heated, changes to
weakly-basic polyoxyethylene derivatives of tri-
ethanolamine.
MANNICH-TYPE REACTIONS
Monoethanolamine and diethanolamine were found to
take part in the Mannich reaction when treated with
an aldehyde or a reactive methyl ketone, β-ketoester,
phenol, or substituted phenol. It is, therefore, possible
to prepare hydroxybenzylaminoethanols from phenols.
Best results occur when the reaction is carried out
with stoichiometric amounts of formaldehyde, phenol,
and ethanolamine. Use of excess formaldehyde or
temperatures near 100°C results in extensive resin
formation because amines will also catalyze phenol-
formaldehyde condensation reactions. Resin forma-
tion is decreased and yields are improved through the
use of alkyl-or aryl-substituted phenols.
AMINONITRILE FORMATION
Either monoethanolamine or diethanolamine, usually as
the hydrochloride, reacts smoothly at room temperature
with an alkali cyanide and one of a variety of aldehydes
or ketones to yield the expected substituted aminoace-
tonitrile. The latter may be saponified in good yield to
the substituted aminoacetic acid.
Similarly, acrylonitrile will react with monoethanolamine or
diethanolamine at room temperature in the absence of
catalysts to give nearly quantitative yields of the N-cya-
noethyl derivatives. When heated, these products decom-
pose to the ethanolamines and acrylonitrile polymers.
27
 Chemical Properties Continued

A number of other α-β-unsaturated compounds are
reported to react similarly.
Triethanolamine does not react with acrylonitrile to give
N-cyanoethyl derivatives. Acrylonitrile will add to the
hydroxyl groups of triethanolamine in the presence of
basic catalysts at moderate temperatures (20 to 40°C).
However, when triethanolamine was poured over pul-
verized potassium permanganate, the reaction was vig-
orous and the mixture burst into flame. Triethanolamine
affords fair yields of the amine oxide when treated with
aqueous hydrogen peroxide or sodium hypochlorite.

OXAZOLINES AND THIAZOLINES

A variety of 2-substituted Δ2-oxazolines may be pre-

OXIDATION pared from the ethanolamides of aliphatic and aromatic
acids, by dehydration at elevated temperatures.
The oxidation of monoethanolamine with an acid solu-
tion of potassium permanganate is reported to give
50% yield of glycine (NH2CH2COOH).

Glycine can also be prepared by heating the

monoethanolamine above 200°C with excess potas-
sium hydroxide. By this method, the yield of glycine is
about 40%, based on monoethanolamine.
A dehydrating agent such as phosphorous pentoxide
This procedure can also be used with the other may be necessary with ethanolamides of aromatic
ethanolamines to obtain the corresponding aminoacetic acids. A similar procedure in the presence of phospho-
acid. The reaction is illustrated with triethanolamine. rous pentasulfide leads to the Δ2-thiazolines.

Monoethanolamine and diethanolamine are oxidized to

formaldehyde and ammonia by periodates in acid solu-
tions. The reaction is quantitative and fairly rapid.
Triethanolamine does not react at an appreciable rate.

28
With carbon disulfide, monoethanolamine gives 2-mercap-
tothiazoline, an accelerator for the vulcanization of rubber.
OXAZOLIDINES AND OXAZOLIDONES
Oxazolidines (tetrahydrooxazoles) substituted in the 2-
position are conveniently prepared by heating
monoethanolamine with an aldehyde or ketone. The
intermediate Schiff’s base is formed with the elimination
of water, after which cyclization occurs, frequently in
good yield. Water is usually removed as the benzene or
butanol azeotrope. Oxazolidines are rather unstable,
easily cleaved by dilute acid to the original reactants,
and usually exhibit the reactions of the intermediate
Schiff’s bases.
When monoethanolamine or diethanolamine is heated
with diethyl carbonate in the presence of an alkaline
catalyst, ethyl alcohol distills from the reaction mix-
ture, leaving oxazolidone-2 or its N-ß-hydroxyethyl
derivative, respectively.
IMINES
Ethylenimine has been prepared by heating the
hydrochloride of β-chloroethylamine with excess
aqueous caustic, but is obtained in best yield by
dropping cold, neutralized solutions of β-aminoethyl-
sulfuric acid into boiling aqueous caustic solutions.
FORMATION OF CYCLIC UREAS
When monoethanolamine and urea are heated gradual-
ly from 110°C to 240°C over a period of eight hours, a
55% yield of ethylene urea may be isolated from the
reaction product. Nitroderivatives of ethylene urea are
of interest as explosives.
MORPHOLINE
Diethanolamine undergoes an intramolecular dehy-
dration to morpholine when mixed with strong sulfu-
ric acid and heated to about 185°C. Hydrochloric
acid is a less satisfactory condensing agent.
The free base is recovered from the crude reaction
product by distillation following the addition of alkali.
29
 Chemical Properties Continued

PIPERAZINE AND PYRAZINE REACTIONS AS A REDUCING AGENT

FORMATION AND REDUCTIVE
AMINATION
Piperazine is formed from the dehydration of
monoethanolamine hydrochloride in the presence of
metal halide catalysts, while substituted piperazines
have been obtained from diethanolamine and tri-
ethanolamine by various means. (See section on
“Reactions with acids, acid anhydrides, acid chlorides,
and esters”.)
A number of aromatic nitro compounds may be reduced
to the corresponding amino derivatives by refluxing with
ethanolamines. Reduction to the aminobenzenes pro-
ceeds in fair yield when the nitro groups are favorably
situated. The ethanolamines appear to be degraded to
ammonia and acetaldehyde. Azobenzenes may also be
among the reaction products.

Piperazine, ethylenediamine, and diethylenetriamine

have been prepared by continuously passing NH3 and
monoethanolamine in molar ratio of 3.5:1 over a Raney
nickel catalyst under an average pressure of ~1,950 psi
and an average temperature of about 195°C.

Piperazine has been obtained in high yields by reacting

ammonia with diethanolamine in the presence of a
Raney nickel catalyst employing 3 to 15 moles of
ammonia per mole of diethanolamine. Anthraquinone can be reduced to anthranol under similar
conditions. Best results are obtained using
Preparation of piperidones, triazones, and thiazanium diethanolamine, although the yields are not impressive.
chlorides has also been recorded.
REACTION WITH ACETYLENE

Monoethanolamine in benzene solution is reported to

react with acetylene in the presence of potassium
hydroxide at 100 to 140°C to give a low yield of the
vinyl ether of ethanolamine. The reaction is complicated
by the formation of other products such as morpholine,
pyridine derivatives, and considerable tar.

30

GENERAL
Handling and storage of the ethanolamines present no
unusual problems. See the section on Toxicity and
Safety, or contact our Technical Services staff for addi-
tional information.
Commercial monoethanolamine, diethanolamine, and
triethanolamine will normally solidify at or slightly below
room temperature. Of the three, diethanolamine has the
highest freezing point.
Triethanolamine, because it normally contains some
monoethanolamine and diethanolamine, may tend to
stratify when stored at temperatures below 60°F. If
this occurs, homogeneity can be restored by warming
and agitating.
The vapor pressure of each of the three ethanol-
amines is less than 1 mm Hg at 20°C. Being organic
compounds, they will undergo combustion, but are
not classified as flammable by the Department of
Transportation.
Although not considered poisonous, the ethanolamines
have toxic properties; they should not be ingested or
allowed to come into repeated or prolonged contact
with the skin. In case of contact with eyes, flush imme-
diately with plenty of water for at least 15 minutes and
get medical attention.
MAINTAINING SPECIFICATIONS
Monoethanolamine is hygroscopic and when exposed
to a moist atmosphere may appear to fume.
Diethanolamine and triethanolamine are also hygroscopic,
but to a lesser degree. If the water content of the
ethanolamine is to be minimized, a dry inert gas pad,
Handling & Storage
such as nitrogen, under a few ounces of pressure
should be used on storage tanks.
Similarly, a gas pad should be used if low color is
important since absorbed atmospheric oxygen will
cause all ethanolamines to develop color. Since
ethanolamines are basic, they will react with acidic
gases, hence carbon dioxide and natural gas containing
acidic sulfur compounds cannot be used.
Ethanolamines should not be used in tanks made from
zinc, galvanized steel or copper and its alloys since
ethanolamines react with copper to form complex salts.
Other factors which should be considered in the instal-
lation of storage and handling facilities are the solvent
properties and alkaline nature of the ethanolamines.
Carbon steel storage tanks constructed according to a
recognized code are generally satisfactory. In cases
where low color or low iron content is important, alu-
minum or stainless steel is preferred.
Aluminum will react with the ethanolamines at elevated
temperatures or in the presence of water. Therefore, it
should not be used to store aqueous blends or in the
construction of steam coils.
The coils should be stainless steel and have an area
sufficient to heat the tank contents using low-pressure
steam. They should be built into the tank about six
inches above the floor and constructed in such a
manner as to allow the condensate to drain. If steam
heat is to be used continuously to prevent freezing of
the ethanolamines, a temperature regulator which
throttles either the steam or condensate should be
installed. The product temperature should not be
allowed to exceed 100°F. High temperatures will cause
31
 Handling & Storage Continued
the amine to become discolored. In situations where
the ambient temperature is low, insulating the tank will
probably be desirable.
If a dry gas pad is used, pressure relief and vacuum
relief valves of suitable capacities should be installed.
The dry-gas system may consist of a cylinder of nitro-
gen, a pressure reducing valve, a pressure relief valve,
and a line to the top of the storage tank. Tankage should
be diked and electrically bonded and grounded.
TRANSFER LINES
Carbon steel transfer lines of preferably not less than 2-
inch diameter, and joined by welds or flanges, are suit-
able. Screwed joints are subject to failure unless back-
welded because ethanolamines will leach conventional
pipe dopes. Flexitallic Type RO-TT mechanical seal, or
equivalent is suitable.
If the ambient temperature is low, the transfer line
should be steam-traced and insulated.
Steam-tracing can be accomplished by fixing copper
tubing, approximately 3/8-inch diameter, to the underside
of the line, insulating the tube to the line, and using low-
pressure steam or hot water in the tubing. For flexible
connections, stainless steel metal hose is preferable to
rubber, since rubber will generally deteriorate in
ethanolamine service.
Systems which are insulated and steam-traced
should be preheated in cool weather before being
put into service.
Normally 15 to 30 minutes of applying steam to the
tubing will adequately warm, but not overheat, the
system.
32
Transfer piping and pumps may be equipped with an
inert gas padding system so that the ethanolamine can
be pressured out of the lines when an extended idle
period is due.
This practice will help reduce the color increase which
would result if the ethanolamine was allowed to lie in
the lines.
PUMPS
All-iron rotary or centrifugal pumps can be used with
the ethanolamines, although a centrifugal pump is pre-
ferred. Rotary pumps, if used, should be equipped with
externally lubricated bearings. A Durametallic Type RO-
TT mechanical seal or equivalent is suitable. Teflon® or
polypropylene are acceptable gasket material for
amines use. Elastomers such as neoprene or Viton®
should be avoided.
Provision should be made for preheating pumps which
are exposed to the cold. This can be done by playing
live steam on the uninsulated pump or by insulating the
pump, wrapping it with copper tubing, and applying
low-pressure steam to the tubing.
UNLOADING IN COLD WEATHER
Thawing a tank or a tank car of one of the
ethanolamines is accomplished by applying steam to
the coils of the tank or tank car. The liquid temperature
should be kept below 100°F.
As the material melts, solids will remain on the bottom
and sides of the tank while the warmer liquid rises.
Thawing may be accelerated by using a liquid circulat-
ing pump. When the tank car is unloaded or when
steam is being discontinued to the tank, the coil should
be blown free of condensate with dry air to prevent
freezing of the condensate and possible coil rupture.
For further information on handling frozen liquids in
tanks, it is recommended that reference be made to
Association of American Railroads’ Pamphlet No. 34,
General American Transportation Corporation’s “Care of
Heater Coils in Tank Cars”.
Ethanolamines which have frozen in drums may be
thawed in a hot room at about 100°F. Thawing should
be expected to require two days.
NEW FACILITIES AND CLEANING
Prior to putting storage vessels into service, it is desir-
able to purge with inert gas to remove oxygen from the
tank atmosphere.
Although frequent cleaning of the tanks and transfer
lines is not recommended, cleaning is sometimes nec-
essary due to contamination or accumulation of foreign
materials in the system. For such cleaning, a water
wash is generally satisfactory.
Tank cleaning is normally accomplished by thoroughly
sluicing the interior of the tank with a water jet, followed
by cloth or chamois drying.
Unless excessive rust scale makes it necessary, the
interior of the tank should not be wire-brushed or
sand-blasted because the oxides of iron are relatively
inert to ethanolamines.
Once clean and dry, the tank should be sealed and
purged with dry inert gas to avoid undue condensation
and rust formation.
New systems frequently introduce line scale, rust, and
the like which will be a source of contamination and
possible plugging. These solids can be effectively
removed with either a “y” strainer, using a 150-to 200-
mesh stainless steel screen or with a commercial-type
cloth filter. A good grade of woven cotton canvas, 12-
ounce or heavier, is suitable as a cloth filter medium.
Wool and synthetic filters have been unsatisfactory.
Most requirements described so far concern the com-
mercial, essentially anhydrous, ethanolamines. Their
aqueous solutions have lower freezing points and lower
viscosities, so storage and handling may be simplified
considerably by dilution in storage if the ethanolamine is
to be used as an aqueous solution.
33
 Health & Safety Continued
MONOETHANOLAMINE
Acute/Short-Term Studies
Acute toxicity tests using monoethanolamine (MEA)
indicate that this material is slightly toxic by a single
oral or dermal exposure. Reported oral LD50 (rat)
determinations range from 1.7 to 2.7 g/kg; the dermal
L50 (rabbit) is reported to be 1 g/kg.
Eye irritation studies (rabbit) produced severe injury to
the eye, including extreme conjunctival irritation,
corneal damage, and necrosis, from administration of
undiluted MEA. Dermal irritation studies (rabbit) demon-
strated extreme dermal irritation and necrosis from a
single application of undiluted MEA. In these studies,
MEA was considered to be corrosive to the skin.
Developmental and Subchronic Studies
Mankes (1986), using unconventional criteria to define
malformations, as well as an unconventional statistical
treatment of the study data, reported that MEA pro-
duced developmental toxicity in rats.
When the data are examined by conventional statistical
treatment, effects are observed across all study groups,
including controls. The true significance of the data is
not clear, since a full reinterpretation of this study by
conventional criteria is not possible at this time.
A short-term screening study for developmental
effects (Periera, et al.,1987) demonstrated that MEA
reduced the number of viable litters, but had no effect
on other measured parameters. While the results of
this screen are suggestive of developmental toxicity in
a longer term, definitive assay, the authors considered
MEA to have a low priority for further testing. To clarify
the potential developmental toxicity of MEA, the
34
Huntsman Corporation and the other members of the
CMA Alkanolamines Panel have sponsored definitive
developmental toxicity studies in rats and rabbits.
In the rat developmental toxicity study, pregnant rats
were dermally exposured to MEA during gestation
days 6 through 15 at dosage levels of 10, 25, 75 and
225 mg/kg/day. Significant maternal toxicity (reduced
body weight gain and skin irritation/crusting) was
observed only at the highest dosage level (225
mg/kg/day).
Despite the observed maternal toxicity, there were no
treatment-related developmental effects observed at
any dosage level in this study.
In the rabbit developmental toxicity study, pregnant
rabbits were dermally exposured to MEA during gesta-
tion days 6 through 18 at dosage levels of 10, 25 and
75 mg/kg/day. Significant maternal toxicity (severe skin
irritation/ crusting) was observed at the highest
dosage level (75 mg/kg/day), although minor skin irri-
tation was also observed in a few does of the 25
mg/kg/day group.
Despite the observed maternal toxicity, there were no
treatment-related developmental effects observed at
any dosage level in this study.
In a subchronic (90-day) oral toxicity study in rats, the
no effect level (NOEL) was determined to be 0.32 g/kg.
Changes to liver and kidney weights were observed at
0.64 g/kg, and histopathological changes in the liver
and kidney and some deaths were observed at 1.28
g/kg. The oral LD50 determined in this study was 2.74
g/kg. (Smyth, et al.,1951.)
Genetic Toxicity
MEA did not demonstrate genotoxic activity when
tested in an in-vitro mutagenicity (Ames) assay.
Health and Safety Information
While the acute oral and dermal toxicity of MEA is
considered slight, the irritating and corrosive proper-
ties of this material may result in serious injury from
amounts that might be accidentally ingested, splashed
upon the skin or into the eyes, or inhaled.
Certain preexisting medical conditions may be aggravat-
ed by exposure to MEA, such as dermatitis through der-
mal exposure, or respiratory conditions, such as asthma,
bronchitis, and inflammatory or fibrotic respiratory dis-
ease through inhalation of MEA vapors, dust, or mist.
To prevent serious injury when handling MEA, chemi-
cal goggles with face shields, gloves, and protective
clothing should be worn.
Materials for gloves and protective clothing proven to
be satisfactory include the following (breakthrough
times are shown in parentheses): butyl rubber (>8 hr),
neoprene (>8 hr), and Viton (>8 hr). Contact lenses
should not be worn.
When handling large quantities subject to splashes and
spills, impervious suits, gloves, and boots must be worn.
Supplied air respiratory protection is recommended for
cleaning large spills, or on entry to confined, poorly
ventilated areas.
Should contact with the eyes occur, immediately flush
eyes with large amounts of running water for at least
15 minutes.
Eyelids should be held apart while flushing. Get imme-
diate medical attention. If medical attention is not
immediately available, continue flushing with water for
an additional 15 minutes.
If skin contact occurs, immediately flush skin with
large amounts of running water for at least 15 min-
utes. Remove contaminated clothing and shoes. Get
medical attention immediately.
Clothing should be washed before reuse. Nonresistant
footwear should be destroyed.
If MEA is accidentally ingested and the individual is
conscious and can swallow, give two glasses of water
(16 oz). Do not induce vomiting. Get immediate med-
ical attention. Never give anything by mouth to an
unconscious or convulsing person.
Although MEA vapors, dusts, and mists do not readily
develop due to the low vapor pressure of this material,
if MEA is accidentally inhaled the individual should be
moved to fresh air. If the individual is not breathing,
give artificial respiration. If breathing is difficult, or
cyanosis (blue discoloration of skin or lips) is noted,
qualified personnel may administer oxygen. Get imme-
diate medical attention.
Exposure Standards
Occupational exposure standards have been estab-
lished for monoethanolamine. Both the Occupational
Safety and Health Administration (OSHA) and the
American Conference of Governmental Industrial
Hygienists (ACGIH) recommend 3 ppm as the permis-
sible exposure limit, calculated as a time-weighted
35
 Health & Safety
average, and a short-term exposure limit (STEL) of 6
ppm. For transportation purposes, MEA is classified
as a “Corrosive Material” by DOT. A “Corrosive” label
is required for shipping MEA.
Environmental Assessment
Using certain known physical parameters of MEA,
such as water solubility and vapor pressure, a com-
puter simulation of the partition of MEA in the environ-
ment predicts that MEA should partition primarily into
the aqueous component, and is expected to be
mobile in soil, and not expected to absorb to sus-
pended solids or sediment in water. MEA readily
undergoes biodegration and is not expected to persist
in the environment.
Twenty day BOD values ranged from 40 to 67%
biodegradation, Modified Sturm Test showed 97% biode-
gration in 28 days, and a Modified OECD Screening Test
showed 94 to 99% biodegration in 28 days.
MEA is not expected to bioaccumulate in aquatic
organisms with a log octanol:water partition coefficient
(log Kow) of -1.23. MEA has demonstrated a relatively
low degree of toxicity to aquatic organisms: the acute
fish toxicity (LC50) ranges from over 150 to over 300
mg/l (practically non-toxic), the acute Daphnia magna
toxicity (EC50) is greater than 100 mg/l (practically
nontoxic) and the acute algae toxicity (LC) ranges from
1 to 10 mg/l (moderately toxic).
For additional information on the safe handling and
use of Huntsman monoethanolamine products, please
request the appropriate Material Safety Data Sheet.
36
DIETHANOLAMINE
Acute/Short-Term Studies
Acute toxicity tests using diethanolamine (DEA) indicate
that this material is moderately toxic by a single oral
exposure, and practically nontoxic by a single dermal
exposure.
Reported oral LD50 (rat) determinations range from
0.7 to 2.8 g/kg; the dermal LD50 (rabbit) has been
reported to be greater than 12 g/kg.
Although DEA is generally considered to be less irritat-
ing to the eyes and skin than MEA, administration of
undiluted DEA to the eyes of rabbits produced ocular
effects similar to those observed for MEA: severe
injury to the eye, including extreme conjunctival irrita-
tion, corneal damage, and necrosis.
Dermal irritation studies (rabbit) demonstrated slight to
moderate irritation from a single application of undilut-
ed DEA. In these studies, DEA was not considered
corrosive to the skin.
Developmental, Subchronic, and Chronic Studies
A short-term screening study for developmental
effects (Periera, et al.,1987) demonstrated that DEA
reduced the number of viable litters, the percent sur-
vival of the pups, and the weight gain of the pups. The
results of this screen are suggestive of developmental
toxicity in a longer term, definitive assay.
The authors considered DEA to have a high priority for
further testing.
To clarify the potential developmental toxicity of DEA,
the Huntsman Corporation and other members of the
CMA Alkanolamines Panel have sponsored definitive
developmental toxicity studies in rats and rabbits.
In the rat developmental toxicity study, dermal expo-
sures of 150, 500 or 1500 mg/kg/day did not result in
any embryotoxicity.
However, there appeared to be a general delay in ossi-
fication (formation of hard bone structure) in the skulls
of the offspring. The significance of this finding is not
clear, since this effect was only observed in the high-
dose group where maternal toxicity (reduced body
weight gain, severe skin irritation/crusting, increased
kidney weights and anemia) was also observed.
In the rabbit developmental toxicity study, dermal
exposures of 35, 100 or 350 mg/kg/day resulted in
maternal toxicity (severe skin irritation, and increased
kidney and liver weights) in the high-dose group.
Despite the observed maternal toxicity, there were no
treatment-related developmental effects observed in
the offspring.
Subchronic (90-day) exposure studies have been con-
ducted by the National Toxicology Program (NTP) to
investigate potential health effects from repeated oral
and dermal exposures to DEA.
These studies, conducted in both rats and mice, indi-
cated that the kidney, liver, and blood (anemia) were
the primary target tissues for DEA toxicity, as well as
the dermal irritation noted at the treatment sites of
dermal exposures.
In addition, effects in the brain and spinal cord of rats
and the hearts of mice were observed only at extremely
high dosages of DEA. Effects on several other tissues
were reported, although these occurred only at dose
levels which produced severe debilitation of the animals
and were considered secondary effects by NTP.
Furthermore, most of the effects reported in these
studies were observed only in one species tested, and
a clear dose-related response was not always evident,
making the relevance of these findings across species
questionable.
Chronic dermal exposure studies in rats and mice,
sponsored by the NTP, have shown that mice dermally
exposed to DEA showed an increased incidence of
liver tumors in both male and female mice, as well as
an increased incidence of kidney tumors in male mice.
In contrast to the mice, male and female rats dermally
exposed to diethanolamine did not show an increased
incidence of tumors.
In their study report, NTP has concluded that there is
“no evidence” of cancer in male and female rats, and
“clear evidence” of liver and kidney cancer in male mice,
and “clear evidence” of liver cancer in female mice.
The CMA Alkanolamines Panel, with the cooperation
of the NTP, has investigated the conduct of this study
and has concluded that the experimental design of the
study was seriously flawed.
In addition, the results of this NTP study are not con-
sistent with other scientific studies investigating the
carcinogenic potential of DEA.
The flawed experimental design of this mouse study,
as well as the inconsistency of the NTP mouse study
37
 Health & Safety Continued
results with other studies, raises a legitimate question
about the relevance of the NTP study to establish the
risk of cancer in humans from exposures to DEA.
The CMA Alkanolamines Panel convened a panel of
independent research experts to help design a
research program for DEA, investigating the role of
nongenotoxic mechanisms of carcinogenicity as it
applies to the DEA exposures in the NTP study.
Results from this research program indicate that mice
administered DEA via oral and dermal routes of expo-
sure had significantly lower levels of choline and phos-
phocholine. Other research has shown that rats fed
choline deficient diets, resulting in choline/phospho-
choline deficiency, develop liver tumors.
In addition, rodents are expected to be more sensitive
to choline depletion relative to humans due to differ-
ences in metabolism between rodents and humans.
Additional research in this area is still underway, and
the results of all of the DMA Alkanolamines Panel
research will be published upon the conclusion of this
research program.
Genetic Toxicity
DEA did not demonstrate mutagenic activity when
tested in an Ames Assay or the mitotic gene conver-
sion assay in yeast. In addition, DEA did not induce
DNA repair in rat liver cells, nor did it induce sister
chromatid exchange (SCE), chromosomal aberrations,
or cell transformation in cultured hamster cells.
Health and Safety Information
While the acute oral toxicity of DEA is considered mod-
erate and the dermal toxicity is minimal, the irritating
38
properties of this material may result in serious injury
from amounts that might be accidentally ingested,
splashed upon the skin or into the eyes, or inhaled.
Repeated dermal contact may result in a persistent
irritation or dermatitis and should be avoided.
Certain preexisting medical conditions, such as dermati-
tis, may be aggravated by dermal contact with DEA.
To prevent serious injury when handling DEA, chemical
goggles with face shields, gloves, and protective
clothing should be worn.
Materials for gloves and protective clothing proven to
be satisfactory include the following (breakthrough
times are shown in parentheses): butyl rubber (>8 hr),
neoprene (>8 hr), nitrile (>8 hr), Viton (>8 hr), and PVC
(>4 hr). Contact lenses should not be worn.
When handling large quantities subject to splashes
and spills, impervious suits, gloves, and boots must
be worn. Supplied air respiratory protection is recom-
mended for cleaning large spills, or on entry to con-
fined, poorly ventilated areas.
Should contact with the eyes occur, immediately flush
eyes with large amounts of running water for at least
15 minutes.
Eyelids should be held apart while flushing. Get imme-
diate medical attention. If medical attention is not
immediately available, continue flushing with water for
an additional 15 minutes.
If skin contact occurs, wash skin with plenty of soap
and water until all traces of material are removed.
Remove contaminated clothing and shoes. Get med-
ical attention if skin irritation persists, or if skin contact
has been prolonged.
If DEA is accidentally ingested and the individual is
conscious and can swallow, give two glasses of water
(16 oz). Do not induce vomiting. Get immediate med-
ical attention. Never give anything by mouth to an
unconscious or convulsing person.
Although DEA vapors, dusts, and mists do not readily
develop due to the low vapor pressure of this material,
if DEA is accidentally inhaled and symptoms of respi-
ratory tract irritation, headache, nausea, or drowsiness
occur, the individual should be moved to fresh air. Get
medical attention if breathing becomes difficult or
symptoms persist.
Exposure Standards
Occupational exposure standards have been estab-
lished for diethanolamine. OSHA recommends 3 ppm
as the permissible exposure limit, calculated as a time-
weighted average. ACGIH recommends 2 mg/m3 as
the permissible exposure limit, also calculated as a
time-weighted average, and includes a “skin” notation
with this permissible exposure limit.
Environmental Assessment
Using certain known physical parameters of DEA,
such as water solubility and vapor pressure, a com-
puter simulation of the partition of DEA in the environ-
ment predicts that DEA should partition primarily into
the aqueous component, and is expected to be
mobile in soil, and not expected to absorb to sus-
pended solids or sediment in water.
DEA readily undergoes biodegration and is not expect-
ed to persist in the environment. Twenty day BOD val-
ues ranged from 40 to 67%, Modified Sturm Test
value was 97% in 28 days, and a Modified OECD
Screening Test was 100% in 19 days.
On the basis of the log octanol:water partition coeffi-
cient (log Kow = -1.43), DEA is not expected to bioac-
cumulate in aquatic organisms. The acute fish toxicity
(LC50) ranges from over 100 to over 5000 mg/l (practi-
cally non-toxic); the acute Daphnia magna toxicity
(EC50) is greater than 100 mg/l (practically nontoxic)
and the acute algae toxicity (EC50) ranges from 3.3 to
10 mg/l (moderately toxic).
For additional information on the safe handling and
use of Huntsman ethanolamine products, please
request the appropriate Material Safety Data Sheet.
TRIETHANOLAMINE
Acute/Short-Term Studies
Acute toxicity tests using triethanolamine (TEA) indi-
cate that this material is practically nontoxic by a sin-
gle oral or dermal exposure. Reported oral LD50 (rat)
values range from 4.2 to 11.2 g/kg; the dermal LD50
(rabbit) is reported to be greater than 2 g/kg.
TEA is much less irritating to the eyes and skin than
DEA or MEA; administration of undiluted TEA to the
eyes of rabbits produced slight irritation. A single
application of undiluted TEA produced slight irritation
in dermal irritation studies (rabbit).
The absence of dermal sensitization potential for TEA
has been established in several guinea pig assays.
Dosages in these assays ranged from 5% aqueous
solution to undiluted.
39
 Health & Safety Continued
Subacute (14-day) exposure studies have been con-
ducted by the National Toxicology Program (NTP) to
investigate potential health effects from short-term,
repeated, oral, dermal, and inhalation exposures to TEA.
Body weight decreases and deaths were noted in the
dosed-water rat study, but these findings were attributed
to severe dehydration due to palatability problems with
the dosing solutions. None of these studies produced
consistent treatment-related findings, with the exception
of anticipated upper respiratory tract irritation and inflam-
mation in the inhalation studies, and the dermal effects
noted in the dermal exposure studies.
Developmental, Subchronic, and Chronic Studies
Although definitive developmental toxicity tests have
not been performed with TEA, a short-term screening
study for developmental effects (Periera, et al.,1987)
demonstrated that TEA did not produce any evidence
of maternal toxicity or fetal effects at the concentration
tested (1.125 g/kg/day). The NTP has investigated
potential health effects from subchronic (90-day) expo-
sure to TEA. These studies conducted in both rats
and mice, produced principally dermal effects resulting
from exposure to TEA.
Although other effects were observed, histopathological
evaluations did not confirm underlying lesions for these
effects. Smyth, et al.,1951, in a subchronic (90-day)
feeding study in rats, demonstrated a NOEL of 0.08
g/kg. Alterations to liver and kidney weights occurred at
0.17 g/kg, and microscopic lesions and death of some
study animals were observed at 0.73 g/kg.
Several investigators have investigated the effects from
chronic exposure to TEA. In 1978, Hoshino and
Tanooka investigated the carcinogenicity of TEA in
40
ICR-JCL mice using TEA in the diet. Although there
was an increase in the number of Iymphomas in the
female exposure groups, this increase is considered to
be artifactual in nature.
Reviewers of this study have noted that the incidence
of spontaneous tumors in the control groups was usu-
ally low. The number of Iymphomas in the treatment
groups was not dose-dependent, and their incidence
was low.
The conclusion of the reviewers was that the artifactu-
al increases in tumors was indicative of spontaneous
tumors in an old population of animals. In 1986,
Maekawa, et al., investigated the carcinogenicity of
TEA in drinking water when administered to rats. The
results of this study demonstrated kidney effects from
chronic exposure to TEA, but no evidence of carcino-
genicity. A subsequent paper by Konishi, et al., 1992,
demonstrated that the chronic administration of TEA in
drinking water at 2% was not carcinogenic to mice.
There was no significant increase in tumors in compar-
ison to control groups. In this study, no significant
changes were observed in organ weights. However, a
general decrease in body weights was observed in the
high-dose group (2% TEA) when compared to the
control group. The Konishi data clearly support TEA as
noncarcinogenic to mice.
The consensus of the available data on the oral car-
cinogenicity of TEA, along with reviewers’ comments,
indicate that TEA is not carcinogenic to rats or mice,
when provided in the diet or by drinking water.
A chronic (lifetime) dermal exposure study in rats and
mice exposed to triethanolamine (TEA) has been con-
ducted by the National Toxicology Program (NTP). In
the study report, NTP has concluded that there is “no
evidence” of cancer in female rats and the male and
female mouse studies are considered “inadequate”
studies for determining the carcinogenic potential of
TEA, due to the infection of the study animals with a
bacterial infection (Helicobacter hepaticus), an agent
known to cause liver tumors. To clarify the carcino-
genic potential of TEA in mice, NTP is currently spon-
soring repeat male and female mouse carcinogenicity
studies with uninfected animals.
Genetic Toxicity
TEA did not demonstrate mutagenic activity when
tested in the Ames or B. subtilis assays. Although TEA
did not induce chromosomal aberrations or cell trans-
formation in cultured hamster cells, the utility of this
information is limited since there was no exogenous
metabolic activation system included for this culture
system. TEA did not induce DNA repair when tested in
the Unscheduled DNA Synthesis (UDS) assay using rat
hepatocytes.
Health and Safety Information
On the basis of the preceding information, TEA would
not be expected to cause serious injury in amounts
that might be accidentally ingested, splashed into the
eyes or onto the skin, or inhaled. Certain preexisting
medical conditions, such as dermatitis, may be aggra-
vated by dermal contact with TEA. To prevent serious
injury when handling TEA, chemical goggles, gloves,
and protective clothing should be worn. Materials for
gloves and protective clothing proven to be satisfacto-
ry include the following (breakthrough times are shown
in parentheses): butyl rubber (>8 hr), neoprene (>8 hr),
nitrile (>8 hr), PVC (>8 hr), and natural rubber (>4 hr).
Supplied air respiratory protection is recommended for
cleaning large spills, or on entry to confined, poorly
ventilated areas. Should contact with the eyes occur,
immediately flush eyes with large amounts of running
water for at least 15 minutes. Eyelids should be held
apart while flushing. Get immediate medical attention.
If skin contact occurs, wash skin with plenty of soap and
water for several minutes. Get medical attention if skin
irritation develops or persists. If TEA is accidentally
ingested and the individual is conscious and can swal-
low, give two glasses of water (16 oz), and induce vomit-
ing as directed by medical personnel. Never give any-
thing by mouth to an unconscious or convulsing person.
Exposure Standards
Occupational exposure standards have been estab-
lished for triethanolamine. ACGIH recommends 5
mg/m3 (aerosol) as the permissible exposure limit, cal-
culated as a time-weighted average.
Environmental Assessment
Using certain known physical parameters of TEA, such
as water solubility and vapor pressure, a computer
simulation of the partition of TEA in the environment
predicts that TEA should partition primarily into the
aqueous component, and is expected to be mobile in
soil, and not expected to absorb to suspended solids
or sediment in water.
TEA readily undergoes biodegration and is not expect-
ed to persist in the environment. Twenty day BOD val-
ues ranged from 61 to 69% biodegradation, Modified
Sturm Test showed 100% biodegration in 28 days,
and a Modified OECD Screening Test showed 96%
biodegration in 19 days.
41
 Health & Safety Continued
TEA is not expected to bioaccumulate in aquatic
organisms with a log octanol:water partition coefficient
(log Kow) of -1.75). TEA has demonstrated a relatively
low degree of toxicity to aquatic organisms: the acute
fish toxicity (LC50) ranges from over 200 to over
10,000 mg/l (practically nontoxic), the acute Daphnia
magna toxicity (EC50) is greater than 2000 mg/l (prac-
tically non-toxic) and the acute algae toxicity (E50)
ranges from 470 to 750 mg/l (practically nontoxic).
For additional information on the safe handling and use
of Huntsman triethanolamine products, please request
the appropriate Material Safety Data Sheet (MSDS).
NITROSAMINES
Diethanolamine and triethanolamine can combine with
nitrites and other nitrosating agents under a variety of
conditions to form N-nitrosodiethanolamine (NDELA),
an animal carcinogen.
The International Agency for Research on Cancer
(IARC) has reviewed the available animal toxicity data
for NDELA, and has concluded that there is sufficient
evidence in two experimental animal species that
NDELA is carcinogenic.
42
IARC further cautioned that NDELA “be regarded as if
it were carcinogenic to humans.” Although
monoethanolamine itself has not been found to form a
stable nitrosamine, it can combine with an aldehyde,
such as formaldehyde, and can then be nitrosated to
form a nitrosamine.
It has been recognized that some applications of
amines, including ethanolamines, must be carefully
scrutinized to prevent the formation of nitrosamines by
the process of nitrosation. Careful consideration
should be given to formulations containing
ethanolamines to prevent or minimize the formation of
nitrosamines.
To underscore our concern over the formation of
nitrosamines in formulations using Huntsman
ethanolamine products, these products contain pre-
cautionary language on the product label and in the
MSDS warning of potential nitrosamine formation.
References for toxicological and industrial hygiene
information are available upon request.

Delivery of ethanolamines can be made in bulk or in
drums. Generally, the bulk shipments are by tank car or
tank truck, although larger shipments are available from
our Port Neches, Texas plant.
The tank cars are welded carbon steel construction with
bottom unloading fittings and are insulated, exterior
steam-coil equipped. For low iron products, stainless
steel or lined tank cars with bottom unloading fittings
are available.
In areas within reasonable proximity of bulk storage
points, deliveries can be made in full or compartmented
stainless steel tank truck, equipped with steam coils
and insulation. If requested, tank wagons can also be
equipped with unloading pumps and hoses.
Shipping Information
Drums of the tree ethanolamines can be shipped
promptly in truckload and less-than-truckload quanti-
ties. Net contents of drums are 470, 490, and 520
pounds for monoethanolamine, diethanolamine, and tri-
ethanolamine, respectively. Drums are normally the 55
gallon nonreturnable type.
No warning labels are required for diethanolamine or tri-
ethanolamine. Monoethanolamine requires a “Corrosive”
warning label.
Thawing a tank or a tank car of one of the
ethanolamines is accomplished by slowly applying
steam to the coils of the tank or tank car. The liquid
temperature should be kept below 100°F.
43
 Sales Office
HUNTSMAN
CORPORATION
10003 Woodloch Forest Drive
The Woodlands, TX 77380
Tel: 281-719-6000
Fax: 281-719-6055
Research and Development
Advanced Technology Center
8600 Gosling Roadd
The Woodlands, TX 77381
Tel: 281-719-7400
Fax: 281-719-7500
44
Huntsman International
Trading Corporation
150 Beach Road
Gateway West #37-00
Singapore 189720
Telephone: +65-62973363
Facsimile: +65-62963368
Huntsman International
Trading Corporation
Taiwan Representative Office
11-F4, 30, Sec. 3
Chung Shan N. Road
Taipei, Taiwan R.O.C.
Tel: 886-2-2586-3467
Fax: 886-2-8596-1919
Huntsman do Brasil
Participacoes, Ltda.
807 Conj. 2314
01311-000 San Paulo - SP,
Brazil
Tel: 55 11-253-6448
Huntsman Corporation Europe
Everslaan, 45
3078 Everberg
Belgium
Tel: 32-2-758-9211
Fax: 32-2-758-9946
Huntsman Corporation
Canada Inc.
Box 61128 RPO Kensington,
Calgary, Alberta, T2N 4S6 Canada
Tel: 403-276-1166
Fax: 403-276-1163
Huntsman de Mexico, S.A. de
C.V.
Angel Urraza Num. 303
Col. Insurgentes San Borja
C.P. 03100 Mexico, D.F.
Tel: +52 55 9000 2911
Fax: +52 55 9000 2010
Huntsman Australia
61 Market Road, Brooklyn,
Victoria, Australia, 3012
Tel: 61-3-9316-3646
Fax: 61-3-9316-3647
Emergency Assistance
For transportation emergencies
only, call CHEMTREC 1-800-424-
9300 or 1-800-328-8501.
For all other emergencies, call
409-722-8381, our 24-hour
emergency number in Port
Neches, Texas.
 Copyright © 2006 Huntsman Corporation or an affiliate
thereof. All rights reserved.

Warning: Products manufactured from these chemi-

cals may present a fire hazard if improperly used.
Each manufacturer and user of such products should
determine whether there are potential hazards in a
specific application and take the necessary precau-
tions.

Huntsman Corporation warrants only that its products

meet the specifications stated herein (if any). Typical
properties, where stated, are to be considered as rep-
resentative of current production and should not be
treated as specifications. While all the information pre-
sented in this document is believed to be reliable and
to represent the best available data on these products,
HUNTSMAN MAKES NO WARRANTY OR GUARAN-
TEE OF ANY KIND, EXPRESS OR IMPLIED, INCLUD-
ING BUT NOT LIMITED TO ANY WARRANTY OF
MERCHANTABILITY OR FITNESS FOR A PARTICU-
LAR PURPOSE, NON-INFRINGEMENT OF ANY
INTELLECTUAL PROPERTY RIGHT OF ANY THIRD
PARTY, OR WARRANTIES AS TO QUALITY OR COR-
RESPONDENCE WITH PRIOR DESCRIPTION OR
SAMPLE, AND ANY USER OF PRODUCTS
DESCRIBED HEREIN SHOULD CONDUCT A SUFFI-
CIENT INVESTIGATION TO ESTABLISH THE SUIT-
ABILITY OF ANY PRODUCT FOR ITS INTENDED USE
AND ASSUMES ALL RISK AND LIABILITY WHATSO-
EVER RESULTING FROM THE USE OF SUCH PROD-
UCT, WHETHER USED SINGLY OR IN COMBINATION
WITH OTHER SUBSTANCES. Product(s) described in
this publication may be hazardous and/or toxic and
require special precautions in handling. For all prod-
uct(s) described herein, the user should obtain from
Huntsman detailed information on hazardousness
and/or toxicity, together with proper shipping, han-
dling, and storage procedures, and should comply
with all applicable safety and environmental standards.
The behaviour, hazardousness and/or toxicity of the
product(s) referred to in this publication in manufactur-
ing processes and their suitability in any given end-use
environment are dependent upon various conditions
such as chemical compatibility, temperature, and other
variables, which may not be known to Huntsman. It is
the sole responsibility of the user of such product(s) to
evaluate the manufacturing circumstances and the
final product(s) under actual end-use requirements and
to adequately advise and warn future purchasers and
users thereof.

10003 Woodloch Forest Drive

The Woodlands, Texas 77380
281-719-6000

Huntsman Advanced Technology Center

8600 Gosling Rd.
The Woodlands, Texas 77381
www.huntsman.com 281-719-7400

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