"Ethanolamines and Propanolamines," in: Ullmann's Encyclopedia

� 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Article No : a10_001

Ethanolamines and Propanolamines

MATTHIAS FRAUENKRON, BASF Aktiengesellschaft, Ludwigshafen, Germany

JOHANN-PETER MELDER, BASF Aktiengesellschaft, Ludwigshafen, Germany

GUNTHER RUIDER, BASF Aktiengesellschaft, Ludwigshafen, Germany

ROLAND ROSSBACHER, BASF Aktiengesellschaft, Ludwigshafen, Germany

HARTMUT HOKE, Weinheim, Germany

1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 405

2. Ethanolamines . . . . . . . . . . . . . . . . . . . . . . 405

2.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . 406

2.1.1. Physical Properties . . . . . . . . . . . . . . . . . . . 406

2.1.2. Chemical Properties. . . . . . . . . . . . . . . . . . . 406

2.2. Production . . . . . . . . . . . . . . . . . . . . . . . . . 407

2.3. Quality Specifications. . . . . . . . . . . . . . . . . 408

2.4. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408

2.5. Economic Aspects . . . . . . . . . . . . . . . . . . . 410

3. N-Alkylated Ethanolamines . . . . . . . . . . . . 410

3.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . 411



3.2. Production . . . . . . . . . . . . . . . . . . . . . . . . . 411


3.4. Uses and Economic Aspects . . . . . . . . . . . . 413

4. Isopropanolamines . . . . . . . . . . . . . . . . . . . 414

4.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . 414



4.2. Production . . . . . . . . . . . . . . . . . . . . . . . . . 416


4.4. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 417

5. N-Alkylated Propanolamines and

3-Alkoxypropylamines . . . . . . . . . . . . . . . . 418

5.1. Properties . . . . . . . . . . . . . . . . . . . . . . . . . 418



5.2. Production . . . . . . . . . . . . . . . . . . . . . . . . . 418


5.4. Uses and Economic Aspects . . . . . . . . . . . . 420

6. Storage and Transportation . . . . . . . . . . . . 421

7. Environmental Protection . . . . . . . . . . . . . 421

8. Toxicology and Occupational Health . . . . . 421

8.1. General Aspects . . . . . . . . . . . . . . . . . . . . . 421

8.2. Ethanolamines . . . . . . . . . . . . . . . . . . . . . . 424

8.3. N-Alkyl- und N-Arylethanolamines . . . . . . . 425

8.4. Propanolamines . . . . . . . . . . . . . . . . . . . . . 427

References . . . . . . . . . . . . . . . . . . . . . . . . . 428

1. Introduction

Amino alcohols have been prepared industriallysince the 1930s.However, large-scale productionstarted only after 1945, when alkoxylation withethylene oxide and propylene oxide replaced theolder chlorohydrin route. In industry, aminoalcohols are usually designated as alkanola-mines. Ethanolamines (aminoethanols) and pro-panolamines (aminopropanols) are by far themost important compounds of this group. Bothare used widely in the manufacture of surfactantsand in gas purification [1–6].

2. Ethanolamines

Monoethanolamine [141-43-5] (1) (MEA; 2-aminoethanol), diethanolamine [111-42-2] (2)

(DEA; 2,20-iminodiethanol), and triethanola-mine [102-71-6] (3) (TEA; 2,20,200-nitrilotrietha-nol) can be regarded as derivatives of ammonia inwhich one, two, or three hydrogen atoms havebeen replaced by a CH2CH2OH group.

Ethanolamines were prepared in 1860 byWURTZ from ethylene chlorohydrin and aqueousammonia [7]. It was only toward the end of the19th century that an ethanolamine mixture was

DOI: 10.1002/14356007.a10_001

separated into its mono-, di-, and triethanolaminecomponents; this was achieved by fractionaldistillation.

Ethanolamines were not available commer-cially before the early 1930s; they assumedsteadily growing commercial importance as in-termediates only after 1945, because of the large-scale production of ethylene oxide. Since themid-1970s, production of very pure, colorlesstriethanolamine in industrial quantities has beenpossible [117–119]. All ethanolamines can nowbe obtained economically in very pure form.

The most important uses of ethanolamines arein the production of emulsifiers, detergent rawmaterials, and textile chemicals; in gas purifica-tion processes; in cement production, as millingadditives; and as building blocks for agrochemi-cals [120]. Monoethanolamine is an importantfeedstock for the production of ethylenediamineand ethylenimine.

2.1. Properties

2.1.1. Physical Properties

Monoethanolamine and triethanolamine are vis-cous, colorless, clear, hygroscopic liquids atroom temperature; diethanolamine is a crystal-line solid. All ethanolamines absorb water andcarbon dioxide from the air and are infinitelymiscible with water and alcohols. The freezingpoints of all ethanolamines can be loweredconsiderably by the addition of water. Somephysical properties of ethanolamines are listedin Table 1.

2.1.2. Chemical Properties

Because of their basic amino group and the hydro-xyl group, ethanolamines have chemical propertiesresembling thoseofboth amines andalcohols.Theyform salts with acids, and the hydroxyl grouppermits ester formation. When mono- and dietha-nolamine react with organic acids, salt formationalways takes place in preference to ester formation.With weak inorganic acids, e.g., H2S and CO2,thermally unstable salts are formed in aqueoussolution. This reaction of ethanolamines is the basisfor their application in the purification of acidicnatural gas, refinery gas, and synthesis gas [1], [8].In the absence of water, monoethanolamine anddiethanolamine reactwithCO2 to formcarbamates:

2 HOCH2CH2NHRþCO2!HOCH2CH2CH2NRCOOH� RHNCH2CH2OH

R ¼ H or CH2CH2OH

Triethanolamine does not form a carbamate.By metal-catalyzed amination, the hydroxyl

group of monoethanolamine can be replaced byan amino group to form ethyleneamines such asethylenediamine [107-15-3], diethylenetriamine[111-40-0], piperazine [110-85-0], and ami-noethylethanolamine [111-41-1] [9], [10]:

Table 1. Physical properties of ethanolamines

Compound Mr mp, �C bp

(101.3 kPa), �CDensitya r

(20 �C), g/cm3

Heat of vaporization

(101.3 kPa), kJ/kg

Specific heat cpkJ kg�1 K�1

Cubic expansion

coefficient, K�1

Monoethanolamine 61.08 10.53 170.3 1.0160 848.1 2.72 7.78�10�4

Diethanolamine 105.14 28.0 268.5 1.0912 (30 �C) 638.4 2.73 5.86�10�4

Triethanolamine 149.19 21.6 336.1 1.1248 517.8 2.33 4.82�10�4

Compound Viscosity n20D Surface tension Flash point,b Ignition temperature,c, Temperature class d

(20 �C), mPa � s (20 �C), N/m �C �C

Monoethanolamine 23.2 1.4544 0.049 94.5 410 T2

Diethanolamine 389 (30 �C) 1.4747 0.0477 176 365 T2

Triethanolamine 930 1.4852 0.0484 192 325 T2

aAccording to DIN 53 217.bAccording to DIN 51 758.cAccording to DIN 51 794.dAccording to VDE 0165. Ethanolamines do not belong to any hazard class according to VbF (regulation governing flammable liquids).

406 Ethanolamines and Propanolamines Vol. 13

Considerable quantities of monoethanola-mine are converted into ethylenimine (aziridine[151-56-4]) by adding sulfuric acid and cyclizingthe hydrogensulfatewith sodiumhydroxide or byusing heterogeneous catalysts [121] (! Aziri-dines) [11], [12]:

As primary and secondary amines, monoetha-nolamine and diethanolamine also react with acidsor acid chlorides to form amides. The amine firstreactswith the acid, e.g., stearic acid, to form a salt,which can be dehydrated to the amide by heating:

NH2CH2CH2OHþC17H35COOH!NH2CH2CH2OH �C17H35COOH!HOCH2CH2�NH�CO�C17H35COOHþH2O

When the ethanolamides of fatty acids areheated at fairly high temperature with removalof water, oxazolines are formed:

Formaldehyde reacts withmonoethanolamineand diethanolamine to form hydroxymethylcompounds, which can be reduced to the N-methyl derivatives [14] (see Section 3.2).

Monoethanolamine reacts with carbon disul-fide to form2-mercaptothiazoline [96-53-7] [15]:

The hydroxyl groups of ethanolamines can bereplaced with chlorine by reaction with thionylchloride or phosphorus pentachloride. The chlor-oethylamines formedarehazardousbecauseof theirskin toxicity.For example, tris(2-chloroethyl)aminehas been used as a gas in warfare (N-lost). Bis(2-chloroethyl)amine is obtained in good yield byreaction of diethanolamine with thionyl chloride:

Reaction of triethanolamine with ethylene ox-ide gives unstable alkaline quaternary compoundsand the corresponding stable ethers [122]. Forexample, undistilled triethanolamine preparedfrom mono- or diethanolamine always containssome triethanolamine monoglycol ether [16].

Mono- or diethanolamine can also be used asthe amine component in aminoalkylation, the so-calledMannich reaction, which is very importantin the biosynthesis of many alkaloids [17].

Catalytic dehydrogenation of diethanolamineleads to iminodiacetic acid, an important build-ing block for agrochemicals [120].

N-Nitrosamines can be formed by treatingdiethanolamine or, under suitable conditions,triethanolamine with nitrous acid, nitrites, oroxides of nitrogen. Animal experiments haveshown thatN-nitrosamines are carcinogenic [18].

Monoethanolamine and triethanolamine canform complexes with transition metal ions (e.g.,chromium, copper, nickel, cobalt, and iron); someof these complexes are water-soluble [123–125].

2.2. Production

Ethanolamines are produced on an industrialscale exclusively by reaction of ethylene oxidewith excess ammonia, this excess being consid-erable in some cases [19].

The reaction of ethylene oxide with ammoniatakes place slowly and is accelerated by water.Anhydrous procedures employ a fixed-bed cata-lyst consisting of an organic ion-exchange resinor thermallymore stable acidic inorganic clays orzeolites [20–23].

Vol. 13 Ethanolamines and Propanolamines 407

In all conventional processes, reaction takesplace in the liquid phase, and the reactor pressureis usually sufficiently large to prevent vaporizationof ammonia and ethylene oxide at the reactiontemperature. In current procedures, ammonia con-centrations in water between 50 and 100%, pres-sures up to 16 MPa, reaction temperatures up to150 �C, and an excess up to 40 mol of ammoniapermole of ethyleneoxide are used. The reaction ishighly exothermic; the enthalpy of reaction isabout 125 kJ per mole of ethylene oxide [24]. Thefollowing competing reactions occur:

Side reactions forming tetrakis(hydroxyethyl)ammonium hydroxide or any ethers are of noimportance in the synthesis [126]. The kinetics ofthese reactions have been studied [25].

All the reaction steps have about the sameactivation energy and show a roughly quadraticdependence of the reaction rate on the watercontent of the ammonia – water mixture used.Therefore, product composition depends solelyon the molar excess of ammonia and not on watercontent, reaction temperature, or pressure [26].The product distribution as a function of themolarratio of the reactants is shown in Figure 1 [27].

Unconsumed ammonia andwater are separatedfrom the products in a distillation line downstreamof the reactor and are recycled. In large-scalecontinuous single-line plants, the requirement forlow energy use (i.e., operation with minimumsteam consumption) determines both the transportof heat from the reactor and the design of thethermally integrated distillation line (Fig. 2).

Product distributionof the three ethanolaminescan be controlled by appropriate choice of theammonia : ethylene oxide ratio. A higher dietha-nolamine or triethanolamine content can also be

obtained by recycling monoethanolamine ordiethanolamine to the reactor or by treating themwith ethyleneoxide in a separate unit [127], [128].

For safety reasons, ethylene oxide must bemetered into the ammonia stream; in the reverseprocedure, ammonia or amines may cause ethyl-ene oxide to undergo an explosive polymeriza-tion reaction.

In all industrial processes, complete conversionto the three ethanolamines, without significantformation of byproducts, is achieved. Therefore,feedstock costs are independent of the type ofproductionprocess.On theother hand,manufactur-ing costs and, in particular, energycosts depend to alarge extent on the product composition desired,plant design, and degree of thermal integration.

2.3. Quality Specifications

Today, all ethanolamines are prepared with> 99% purity. Water, the two other ethanola-mines, and a small amount of triethanolamineglycol ether are minor components; all otherimpurities are in the ppm range. Table 2 givesspecifications for commercial ethanolamines.

Purity is determined by gas chromatography,and the residual water content by theKarl Fischermethod. After pretreatment, the N-nitrosaminecontent can also be determined by gas chroma-tography with a thermal analyzer.

2.4. Uses

Surfactants. Ethanolamines are used wide-ly as intermediates in the production of surfac-

Figure 1. Product distribution of monoethanolamine (a),diethanolamine (b), triethanolamine (c), and glycol ethers oftriethanolamine as a function of themolar ratio of ammonia toethylene oxide (EO) in aqueous solution at 100 – 200 �C


tants, which have become commercially impor-tant as detergents, textile and leather chemicals,and emulsifiers [2–6]. Their uses range fromdrilling and cutting oils to medicinal soaps andhigh-quality toiletries [28] (Fig. 3).

Properties of ethanolamine derivatives can bevaried within wide limits by appropriate choiceof the ethanolamine, the acid component, andtheir ratio. Synergistic effects in complex emul-sifier systems can be obtained by simultaneoususe of different combinations of amines andacids. Ethanolamines, particularly triethanola-mine, which had presented problems with regardto color, are now produced in sufficient puritythat no color problems arise when they aretreated with acids or heated [29–32].

Ethanolamine-based surfactants canbe formu-lated as weakly basic or neutral products and aretherefore particularly well tolerated by the skin;this is especially true for triethanolamine soaps.Moreover, they are noncorrosive and can be usedon virtually all textiles without damage. Ethanol-

amine soaps prepared from oleic acid, stearicacid, lauric acid, or caprylic acid are constituentsof many toiletries and medicinal soaps.

Ethanolamine soaps produced from fatty acidsare among the most industrially important emulsi-fiers. They are used in cosmetics [33], polishes,shoe creams, car care products, drilling and cuttingoils, and pharmaceutical ointments. Ethanolaminesoaps combined with wax and resins are used asimpregnating materials, protective coatings, andproducts for the care of textile and leather goods.

Ethanolamine soaps obtained from alkylaryl-sulfonic acids, preferably alkylbenzenesulfonicacids, or from alcohol sulfates are growing

Figure 2. Flow sheet for the production of ethanolaminesa)Aqueous ammonia tank; b)Tubular reactor; c)Ammonia and ammonia solution columns; d)Dehydration column; e)Vacuumfractionation columns

Table 2. Specifications of commercial ethanolamines

Compound Purity,

wt%

r (DIN 51 757),

g/cm3

Color

(DIN-ISO 6271),

APHA

Monoethanolamine > 99 1.016 (20 �C) � 10

Diethanolamine > 99 1.0912 (30 �C) � 20

Triethanolamine > 99 1.1248 (20 �C) � 30 Figure 3. Percentage consumption of ethanolamines accord-ing to use (1996)


steadily in importance and dominate the marketfor household cleansers [34]. The use of linearalkyl groups instead of branched chains in theseproducts has resulted in greater biodegradability.

Fatty acid ethanolamides and products ob-tained by further ethoxylation have foam-stabi-lizing ability and are therefore important addi-tives for detergents [35], [36]. Diethanolamidesobtained from coconut fatty acids and from oleicacid are used industrially. These amideswere firstdescribed in 1937 [37]. Liquid detergents arebased predominantly on triethanolamine [38–40].

In the manufacture of leather, ethanolamine-based chemicals are used for dressing, dyeing,and finishing. For paints and coatings, ethanola-mines are employed both in production and insofteners and paint removers.

Corrosion Inhibitors. Diethanolamine andtriethanolamine are important components ofcorrosion inhibitors, particularly in coolants forautomobile engines, as well as in drilling andcutting oils. They are also employed as additivesin lubricants.

When the corrosion inhibitor sodium nitriteand diethanolamine are used together, N-nitro-samines may form. These nitrosamines are car-cinogenic; therefore, sodium nitrite and dietha-nolamine or triethanolamine should not be usedsimultaneously.

Gas Purification. Large amounts of etha-nolamines, principally diethanolamine, are usedin absorptive gas purification to remove weaklyacidic components. For example, hydrogen sul-fide and carbon dioxide are removed fromnaturalgas, refinery gas, and synthesis gas [1].

Intermediates. A substantial portion of themonoethanolamine is used as a starting materialin the preparation of ethylenimine and ethylene-diamine. Ethylenimine is converted to polyethy-lenimine, an important chemical in paper tech-nology. Diethanolamine is used as a buildingblock for agrochemicals (e.g., Glyphosphate).

Cement Additives. Since the 1960s, aque-ous solutions of triethanolamine and triethano-lamine acetate have been used as milling addi-tives in cement production [41]. During grindingof the clinker in ball mills, the small amount oftriethanolamine added prevents agglomerationand cushioning of the grinding medium by satu-rating the surfaces of the freshly broken particles.Like other milling additives (e.g., various gly-cols), they reduce the power required for millingthe clinker. The milling of virtually all high-quality portland cement involves milling addi-tives. In addition to assisting the milling process,triethanolamine also improves the flow proper-ties and setting behavior of the cement [42].

2.5. Economic Aspects

Large-scale, economical production of ethano-lamines from ethylene oxide and ammonia inlarge, single-line plants has greatly promotedtheir use in many industrial sectors. In 1999,world ethanolamine capacity was about1.09 � 106 t/a (Table 3). About 50% of worldproduction is monoethanolamine; 30 – 35%,diethanolamine; and 15 – 20%, triethanolamine.

3. N-Alkylated Ethanolamines

N-Alkylated ethanolamines are amino alcoholsthat contain a secondary or tertiary nitrogen atomand one or two hydroxyl groups.

Numerous compounds with different proper-ties and uses can be synthesized by varying thealkyl group.

Table 3. Approximate ethanolamine capacity and production in 1998

Capacity, 103 t/a Estimated production,103 t/a

United States 569 456

Mexico 20 19

Western Europe 275 242

Southeast Asia 123 68

South America 30 16.8

Total 1017 759


3.1. Properties


N-Alkylated ethanolamines are generally liquidand have a faint amine-like odor. They tend todiscolor on prolonged storage, especially if ex-posed to air, light, and temperatures above 40 �C.This tendency to discoloration can be reducedsubstantially by the use of additives when puri-fying the products by distillation, or by pretreat-ing the crude products before distillation[43–45]. N-Alkylated ethanolamines are partial-ly to readily soluble in alcohol, water, acetone,glycols, glycerol, and glycol ethers. They areonly sparingly soluble or even insoluble in non-polar solvents, e.g., aliphatic hydrocarbons.2-Dimethylaminoethanol [108-01-0] (N,N-di-methylethanolamine) and 2-diethylaminoetha-nol [100-37-8] (N,N-diethylethanolamine) formazeotropes with water; N-methyldiethanolamine[105-59-9] does not form an azeotrope. All N-alkylethanolamines are hygroscopic and alsoabsorb CO2 from air. Physical properties oftypical compounds are listed in Table 4.


The chemical properties of N-alkylated ethano-lamines are very similar to those of unsubstitutedethanolamines (see Section 2.1.2). They formunstable salts with inorganic acids such as CO2

and H2S [129–131]. Salts with organic acids givea neutral to weakly basic reaction. N-Alkylatedethanolamines also react with acids or acid deri-vatives to give the corresponding esters. Impor-tant products are dimethylethanolamine acrylate[2439-35-2] and diethylethanolamine acrylate[2426-54-2], which are used as intermediates inthe synthesis of flocculating agents.

Secondary N-alkylethanolamines also reactwith acids to form acid amides. The reaction ofN-alkylethanolamines with ethylene oxide togive longer chain alkoxy derivatives gives lowyields.

3.2. Production

Industrially, N-alkylated ethanolamines are pro-duced almost exclusively by batchwise or con-

tinuous reaction of primary, secondary, or terti-ary amines with ethylene oxide [46–48]. Forsafety reasons, ethylene oxide must be added tothe amine, never vice versa (see Section 2.2).Depending on the product involved, reactiontemperature varies from 50 to 170 �C and pres-sure from 0.2 to 4 MPa. Water accelerates thereaction.

Figure 4 shows a flow sheet for the batchwiseproduction of alkanolamines. The procedure isalso suitable for the manufacture of isopropano-lamines (see Chap. 5); in this case, propyleneoxide is used instead of ethylene oxide.

The oxygen-free reaction kettle (a) is filledwith the amine raw material from the stocktank (b); water is added in an amount of 10 –60%, based on the amine; and the kettle isheated to a minimum temperature around50 �C. Metering of ethylene oxide is thenbegun, the feed rate depending on the removalof heat and the operating pressure of thereaction kettle.

The optimum amount of ethylene oxide inrelation to starting amine is determined by cost-effectiveness (byproducts, work-up costs).When addition of ethylene oxide is complete,the minimum reaction temperature is main-tained for some time to ensure that the productdischarged from the reactor is free of ethyleneoxide. The reaction mixture is separated byfractional distillation. Unconverted amine andwater are removed as the first fraction andrecycled to the subsequent batch. Pure alkano-lamines are obtained by distillation under re-duced pressure.

When primary amines are used, a mixture ofN-alkylethanolamines and N-alkyldiethanola-mines is always formed:

The larger the excess of amine, the lower is theproportion of N-alkyldiethanolamines. If N-al-kylethanolamines are desired, a continuous pro-cess is usually preferred for economic reasons.Excess amine is distilled from the reaction prod-uct and recycled.


Table

4.Physicalproperties

ofN-alkylethanolamines

Compound

CASregistry

number

Mr

mp,� C

bp

(101.3

kPa),� C

Density

d)

r,(20

� C)

g/cm

3

Cubic

expansion

coefficient,

K�1

Heatof

vaporization

kJ/kg

Specific

heat,kJ

kg�1K�1

Specific

electrical

conductivity,

W�1cm

�1

Viscosity

(20

� C),

mPa�s

n20 D

Surface

tension

(20

� C),

mN/m

Flash

point,

� C

Ignition

temperature,

� C

Tem

perature

class

Methylethanolamine

[109-83-1]

75.11

ca.�3

159

0.939–

0.942

7.8

�10�4

564.4

2.55

3.33�

10�6

(25

� C)

13.0

1.4389

34.4

(22

� C)

ca.74

350

T2

Methyldiethanolamine

[105-59-9]

119.17

ca.�2

1247

1.038–

1.041

7.5

�10�4

418.7

1.72

8.1

�10�7

101

1.4694

40.9

(20.3

� C)

137

265

T3

Dim

ethylethanolamine

[108-01-0]

89.14

�70a

134

0.887

1.35�

10�3454.3

2.30

3.8

�10�7

3.85

1.4296

27.1

(24.5

� C)

ca.38

235

T3

Diethylethanolamine

[100-37-8]

117.19

�70a

162

0.883–

0.889

1.07�

10�3383.9

2.42

1.1

�10�3

51.4417

29.2

ca.46

260

T3b

n-Butylethanolamine

[111-75-1]

117.19

�2.1

199

0.8917

7.6

�10�4

397.7

2.45

2.9

�10�7

19.7

1.4435

29.9

(22

� C)

85

265

T3

n-Butyldiethanolamine

[102-79-4]

161.25

�45a

ca.270

0.970

7.7

�10�4

329.5

2.26

6.3

�10�7

75.9

1.462

33.9

(22

� C)

130

260

T3

Dibutylethanolamine

[102-81-8]

173.30

�75a

222–234

0.860

8.1

�10�4

277.6

2.32

9.5

�10�7

7.4

1.4444

26.3

(22

� C)

96

240

T3c

Cyclohexylethanolamine

[2842-38-8]

143.23

37.5

235

0.9797

7.6

�10�4

327.2

2.45

2.0

�10�8

317

1.4860

39.5

(25.1

� C)

122

270

T3

Cyclohexyldiethanolamine

[4500-29-2]

187.29

297

1.0339

6.6

�10�4

319.0

2.30

6.6

�10�4

815

1.4930

40.1

172

255

T3

1-(2-H

ydroxyethyl)piperazine

[103-76-4]

130.19

24

112

(1.33kPa)

1.0592

7.5

�10�4

411.1

2.00

6.1

�10�7

1040

1.110

(40

� C)

38.3

135

280

T3

4-(2-H

ydoxyethyl)morpholine

[622-40-2]

131.18

1.5

–2

224

1.0714

8.1

�10�4

342.7

1.91

4.7

�10�5

26.6

1.4783

40.8

113

205

T3

Hydroxyethylaniline

[122-98-5]

137.18

�30a

282–287

1.0954

1.14�

10�3439.2

2.08

102

1.5796

ca.148

410

T2

Ethylhydroxyethylaniline

[92-50-2]

165.24

37

270

1.030

(40

� C)

7.3

�10�4

2.14

86

139

335

T2

N-Ethylethanolamine

[110-73-6]

89.14

�5.8

167

0.914

15.1

78

330

T2

n-Propylethanolamine

[16369-21-4]103.17

�0.5

180–181

84

290

T3

Hydroxyethylpiperidine

[3040-44-6]

129.21

16.7

198–203

0.973

(25

� C)

20.9

1.4804

83

240

T3

Dihydroxyethylaniline

[120-07-0]

181.24

52

346

1.0161

(200

� C)

1.27

(200

� C)

200

380

T2

tert-Butylethanolamine

[4620-70-6]

117.19

40–43

176–177

0.8576

(60

� C)

5.9

(60

� C)

81

345

T2

tert-Butyldiethanolamine

[2160-93-2]

161.25

44–47

136–139

(1.6

kPa)

0.9556

(60

� C)

21.0

(60

� C)

148

300

T3

aPourpoint.

bHazardclassAII(V

bF).

cHazardclassAIII(V

bF).


With secondary amines, only one product isformed:

Trialkylammonium Chlorides yield the cor-responding 2-hydroxyethylammonium chlor-ides. One of the commercially most importantsalts is choline chloride [67-48-1] (! Choline):

Choline chloride can also be prepared fromtrimethylamine and ethylene chlorohydrin, butthis route has no commercial significance.

Another common method of preparing N-alky-lethanolamines is by N-alkylation of ethanola-mines [49]. Methyl derivatives can also beobtained by reactingmonoethanolamine or dietha-nolamine, or their homologues,with formaldehydeand then reducing the hydroxymethyl compound:

Pure components are obtained from the crudeproducts by distillation.

The reaction of epichlorohydrin with aminesto give N-alkylethanolamines is of only minorcommercial importance.


Table 5 lists specifications of commercial pro-ducts. Purity is almost always measured by gaschromatography.

3.4. Uses and Economic Aspects

N-Alkylethanolamines are used mainly as inter-mediates, especially in the production of phar-maceuticals such as the local anesthetics pro-caine (diethylethanolamine 4-aminobenzoate[59-46-1]) and tetracaine (dimethylethanolamine4-butylaminobenzoate [136-47-0]), crop protec-tion agents, and flocculants (dimethylethanola-mine acrylate) [50]. They are also important inthe preparation of chemicals for the paper andleather industries. Use of N-alkylethanolaminesin the production of plastics has risen substan-tially in recent years.

Direct uses of N-alkylethanolamines, espe-cially methyldiethanolamine [51], include gas-purification methods for removing acidic gases

Figure 4. Flow sheet for the batch production of alkanolaminesa) Reaction kettle; b) Ammonia tank; c) Vessel; d, e, f) Storage tanks


(CO2,H2S). Choline chloride is very important inthe animal feedstuff industry (! Choline) [52].World production was ca. 160 000 t/a in 1999.

Annual worldwide demand for N-alkyletha-nolamines (excluding choline chloride) rangesfrom 2 to 15 000 t, depending on the product andapplication. Some products in the category ofmore than 1000 t/a are N,N-dimethylethanola-mine, N,N-diethylethanolamine, 1-(2-hydro-xyethyl)piperazine derivatives, N-methyldietha-nolamine, and N-methylethanolamine.

4. Isopropanolamines

The propanolamines described here are propanolderivatives containing one amino group. Theyhave the following general formulas:

2-Amino-1-propanols (8) and 1-amino-2-pro-panols (9) have been prepared industrially since1937 by reacting propylene oxide with the appro-priate amine. The products aremixtureswhich areprocessed further; the isomer mixtures are notusually separated on an industrial scale. Themost

importantmembers of this class of compounds arethe isopropanolamines, which are used as mix-tures of various isomers. World capacity for iso-propanolamines is estimated at 40 000 t/a.

3-Amino-1-propanol, H2NCH2CH2CH2OH,which is obtained not from propylene oxide butfrom hydrogenation of ethylene cyanohydrin, isdiscussed in Chapter 5.

4.1. Properties


Isopropanolamines are hygroscopic, virtuallycolorless substances with a slight amine-likeodor. They are readily soluble in water, ethanol,

Table 5. Specifications for commercial N-alkylethanolamines

Compound Boiling range 5 – 95 mLa, �C Purityc (min.), % Water contentd, % Colore, APHA

Dimethylethanolamine 133.5 – 135.5 99.8 < 0.05 15

Diethylethanolamine 161.5 – 163 99.5 < 0.05 15

Methylethanolamine 158.5 – 160.0 99.0 < 0.1 10

Methyldiethanolamine 115.5 – 118 99.0 < 0.2 50

4-(2-Hydroxyethyl)morpholine 223 – 225 99.0 0.2 40

1-(2-Hydroxyethyl)piperazine 121 – 123 b 99.0 0.2 40

1-(2-Hydroxyethyl)piperidine 92 – 96 b 99.5 0.1 40

Hydroxyethylaniline 282 – 287 99.0 0.3 100 – 150

Ethylethanolamine 167 99.5 0.2 15

Dibutylethanolamine 226 – 228 99.0 0.2 40

Butylethanolamine 196 – 198 99.5 0.1 15

n-Propylethanolamine 180 – 181 99.5 < 0.1 10

Butyldiethanolamine 264 – 278 99.0 < 0.3 10

tert-Butylethanolamine 178 99.0 < 0.3

tert-Butyldiethanolamine 136 – 139 (1.6 kPa 99.0 < 0.3

aDIN 51 751.bDIN 53 406.cDetermined by gas chromatography.dDetermined by Karl Fischer method.eAccording to DIN-ISO 6271.


glycol, and acetone but only slightly soluble inhydrocarbons and diethyl ether. Monoisopropa-nolamine is more soluble than monoethanola-mine in organic solvents; it forms a miscibilitygap with heptane and toluene.

Diisopropanolamine and triisopropanolamineundergo thermal decomposition above ca. 170 �Cand can therefore be distilled only at reducedpressure. The freezing points of diisopropanola-mine and triisopropanolamine can be greatlydepressed by adding a small amount of water.

All isopropanolamines have at least oneasymmetrically substituted carbon atom and thuscan be optically active. The commercial productsare racemic mixtures.

Important physical data are listed in Table 6and safety data in Table 7.


The properties of amines and alcohols are com-bined in isopropanolamines, and these com-pounds exhibit typical reactions of both func-tional groups; the amino group can be primary,secondary, or tertiary. In chemical behavior,

isopropanolamines differ only slightly from theethanolamines described in Section 2.1.2.

Isopropanolamines react with acidic gases(H2S,CO2) in aqueous solution to form salts,whichdecompose to the starting materials when heated.This effect is utilized in the purification of naturalgas and synthesis gas. The salts of strong acids,such as HCl or H2SO4, are crystalline compounds.

Diisopropanolamine sulfate eliminates waterat elevated temperature to form 2,6-dimethyl-morpholine sulfate [54].

The sodium salt of the sulfuric acid half-esterofmonoisopropanolamine undergoes cyclizationwhen heated, and propylenimine is formed [55]:

Fatty acids, such as stearic acid, react withisopropanolamine at room temperature to formneutral, waxlike isopropanolamine soaps. In reac-tions above 140 �C and with elimination of water,amides are formed preferentially, and minoramounts of fatty esters [56] are produced in a sidereaction. Complete esterification can be effected

Table 6. Physical properties of propanolamines

Compound CAS registry

number

Mr fp, �C bp

(101.3

kPa), �C

r (20 �C,g/cm3

Cubic

expansion

coefficient

(40 – 100�C), K�1

Heat of

vaporization,

kJ/kg

Specific

heat,

kJ kg-1 K-1

Viscosity,

mPa � sRefractive

index nD

1-Amino-2-propanol (d,l) [78-96-6] 75.11 �0.3 159.7 1.4466

(25 �C)2-Amino-1-propanol (d,l) [6168-72-5] 75.11 þ7.5 168.5 1.4481

(25 �C)Monoisopropanolaminea 75.11 þ1.9 159 0.962 8.2�10�4 604 2.73 30 1.4463

(20 �C) (60 �C) (45 �C)Diisopropanolamineb [110-97-4] 133.19 þ38.9 244 0.9842 8.2�10�4 375 2.49 58 1.4542

(60 �C) (60 �C) (60 �C)Triisopropanolamineb [122-20-3] 191.27 ca. 55 291 0.9904 6.9�10�4 309 2.47 141 1.4555

(60 �C) (60 �C) (60 �C)aCommercial isomer mixture consisting of ca. 94 % 1-amino-2-propanol and 6% 2-amino-1-propanol.bCommercial isomer mixture.

Table 7. Safety data for isopropranolamines [53]

Monoisopropanolamine Diisopropanolamine Triisopropanolamine

Flash point, �C 71 135 160

Ignition temperature, �C 335 290 275

Explosion limits, vol % 1.9–10.4 1.6 – 8.0 0.8 – 5.8

Vapor pressure, hPa 1.9 (20 �C) 2.06 (100 �C) 1 (100 �C)


by reaction with acyl chlorides in the presence ofpyridine [57]. The reaction of esters with isopro-panolamines above 100 �C gives amides [58]:

When thionyl chloride is used as a reactantand chloroform as the solvent, the hydroxylgroup can be exchanged for chlorine. Isopropa-nolamine is converted to 2-chloropropylamine[59], which is obtained in good yield.

Isopropanolamine and diisopropanolaminereact with epoxides to give mixed isopropanola-mines. The amino group is several times morereactive than the hydroxyl group [60]. In thepresence of suitable catalysts such as sodiumhydroxide or sodium alkoxides, the epoxide re-acts preferentially with the hydroxyl group toform polyethers [61]. Alkylating substances,e.g., alkyl halides or dimethyl sulfate, give N-alkylated derivatives [62].

Isopropanolamine can be converted to 1,2-diaminopropane by catalytic amination underpressure (! Amines, Aliphatic, Section 8.1.2.).

Aldehydes and ketones react with the primarynitrogen atom of isopropanolamine to form aSchiff base.

CH3CHðOHÞCH2NH2þRCHO!CH3CHðOHÞCH2N

¼ CHRþH2O

Formaldehyde reacts with isopropanolaminesto form the corresponding hydroxymethyl com-pounds, which can be converted to the methylderivatives by catalytic hydrogenation.

Compounds containing an active hydrogenatom undergo a Mannich reaction with formal-dehyde and an isopropanolamine that has a pri-mary or secondary amino group.

ðCH3Þ2C ¼ OþHCHOþHNR1R2

!CH3Cð¼ OÞCH2CH2NR1R2þH2O

R1 ¼ H; C3H6OH;R2 ¼ C3H6OH

Diisopropanolamine reacts with nitrous acidor its salts to form N-nitrosamines. Isopropano-lamines react with optically active acids, such astartaric acid, to form diastereomeric pairs ofsalts; this enables the separation of isopropano-lamines into their enantiomeric forms [63].

The use of triisopropanolamine as an esterifi-cation catalyst has been suggested [64].

4.2. Production

Isopropanolamines are produced like ethanola-mines (see Section 3.2, Fig. 4), by treating pro-pylene oxide with NH3 in the liquid phase in acontinuous or batchwise procedure [65], [66].The product is always a mixture of 1-amino-2-propanols and 2-amino-1-propanols, with the 1-amino isomers being the major component.

Industrially, themanner in which the propyleneoxide ring is cleaved, and hence the isomer ratio ofisopropanolamines, cannot yet be controlled.

Excess ammonia (about 2 – 20 mol permole ofpropylene oxide) facilitates removal of the reactionheat (about 93 kJ/mol) and reduces the amount ofpolypropoxylated byproducts. This amount alsodepends on the relative reaction rates of propyleneoxide with any amines present in the mixture.

Reaction temperatures can vary from 50 to150 �C but are preferably around 100 �C. Theresulting pressure can be reduced by adding water(ca. 10 – 60%). Water and hydroxyl-containingcompounds such as alcohols, phenols, and alkano-lamines (autocatalysis) accelerate the reaction [67].


A continuous procedure is used for large-scale production, e.g., of monoisopropanolamineand diisopropanolamine [68], [69]. This proce-dure is similar to that used to produce ethanola-mines (see Section 2.2).

The most important manufacturers of isopro-panolamines are Air Products, BASF, Bayer,Sasol, and ICI in Western Europe, and DowChemical in the United States.


Because isopropanolamines are manufactured,sold, and used worldwide, the commercial pro-ducts differ only slightly in delivery specifica-tions. Typical specifications are listed in Table 8.

Purity is usually determined by gas chroma-tography. Depending on analytical conditions,isomeric and enantiomeric forms of isopropano-lamines exhibit different numbers of peaks,which can be identified by test analyses. Deri-vatives obtained by reaction with trifluoroaceticanhydride can be analyzed more easily and anal-ysis time can be reduced.

4.4. Uses

Possible uses of isopropanolamines are similar tothose of ethanolamines; as a rule, the isopropano-lamine derivatives exhibit better solubility in hy-drophobicmedia. For example, neutralizationwithfatty acids, such as stearic or lauric acid, gives the

corresponding soaps which are used in lubricantadditives, textile finishing, and coating paper andwood [70]. Salts of isopropanolamines with fattyacids are also used as ionic emulsifiers in emulsionpaints and as dispersants for pigments. Salts ofisopropanolamines with alkylarylsulfonic acidsare employed as degreasers and cleaning promo-ters [71]. The fatty acid amides of isopropanola-mines and mixtures of these with esters are fre-quently used in the cosmetics industry as shampoothickeners and foam regulators [72].

Isopropanolamines are effective corrosion in-hibitors in antifreezes [73] and cutting oils. Si-multaneous use of nitrites should be avoided,since carcinogenic nitrosamines may form undercertain circumstances. Isopropanolamines areimportant catalysts for urethane foams [74]. Inepoxy resin systems, they have proved usefuladditives to curing agents [75].

Sulfur-containing isopropanolamine deriva-tives are used to extract metal ions, such asmercury, gold, and platinum, from salt solutionsand wastewater [76].

A very important use of aqueous diisopropa-nolamine solutions is as a gas wash in the Adipand Sulfinol processes. Here, CO2 and H2S, inparticular, arewashed out of natural gas, synthesisgas, or coke oven gas and, after desorption, can beobtained in some cases in their pure form [77].

Monoisopropanolamine is employed exten-sively as an intermediate in the production of1,2-diaminopropane (! Amines, Aliphatic, Sec-tion 8.1.2.), while diisopropanolamine is used forthe synthesis of 2,6-dimethylmorpholine [54].

Table 8. Minimum quality requirements for commercial isopropanolamines (as of 2000)

Quality criterion Method Monoisopropano-

lamine

Diisopropanolamine Diisopropanolamine

containing 10% H2O

Triisopropanolamine Triisopropanolamine

containing 15% H2O

Water content,

wt %

DIN 51

777

max. 0.2 max. 0.2 10 � 1 max. 0.2 15 � 1

Purity, %* GC min. 99.0 min. 99.0 88 min. 99.0 84

Low boilers

(max.), %*

GC 0.3 0.3 0.3 0.3 0.3

(excluding H2O)

High boilers

(max.) %*

GC 0.5 0.5 0.5 0.5 0.5

Color (max.),

APHA

DIN-ISO

6271

20 50 50 100 100

Acid consumption,

mL of 1 N HCl

per gram

13.15 – 13.45 7.35 – 7.65 6.60 – 6.90 5.10 – 5.40 4.30 – 4.60

Freezing point, �C BS 523 :

1964

ca. 2 ca. 39 ca. �10 ca. 58 < -10

*Determined as area under GC peak.


5. N-Alkylated Propanolamines and3-Alkoxypropylamines

N-Alkylated propanolamines can be divided intoN-alkylated 1-amino-2-propanols, 2-amino-1-propanols, and 3-amino-1-propanols.

2-Amino-1-propanols and 1-amino-2-propa-nols are referred to industrially as isopropanola-mines (Chap. 4).N-Alkylated isopropanolaminesare prepared by reacting propylene oxide with thecorresponding amines, which yields almost ex-clusively 1-amino-2-propanols [78]. Alkylated 2-amino-1-propanols have no industrial importanceand are not discussed in this chapter.

5.1. Properties


With a few exceptions, N-alkylated isopropanola-mines, 3-amino-1-propanols, and 3-alkoxypropy-lamines are colorless liquids at room temperature.Some of them, such as cyclohexylisopropanola-mine, are crystalline solids.Thecompounds tend todiscolor on prolonged storage, especially if ex-posed to light, air, and heat (> 40 �C). They havean amine-like odor, and absorb water and carbondioxide. They are soluble in water, alcohol, ace-tone, glycol, glycerol, and glycol ethers, but onlysparingly soluble in aliphatic or aromatic hydro-carbons and diethyl ether. Methyldiisopropanola-

mine does not form an azeotropewithwater, but anazeotrope is formed upon distillation of aqueousdimethylisopropanolamine and 3-methoxypropy-lamine. Physical properties of N-alkylated isopro-panolamines are given in Table 9 and those of 3-amino-1-propanols and 3-alkoxypropylamines inTable 10.


Because N-alkylated propanolamines contain hy-droxyl groups and basic nitrogen, they possess theproperties of both amines and alcohols. They formsalts with organic and inorganic acids [79]. Thesulfuric acid esters of propanolamines can be cy-clized with sodium hydroxide to give propyleni-mines (see Section 4.1.2) [80]. Propanolamineswith secondary amino groups form alkanolamideswith fatty acids. Reaction of the amides withethylene oxide gives water-soluble or easily dis-persible nonionic surfactants [81]. 1-Amino-2-pro-panols are chiral and can be separated into enan-tiomers bymeansof appropriate reagents [63], [82].N-Alkylpropanolamineswith tertiary aminogroupscan be converted by means of benzoyl chloride,without the assistance of a base, into the aminoalcohol ester hydrochlorides; with thionyl chloride,they give 2-chloropropylammonium chlorides.

The condensation of 3-amino-1-propanolwith carbonyl compounds yields tetrahydro-1,3-oxazines [83], Schiff bases, or mixtures ofboth compounds. 3-Amino-1-propanol and 2-hydroxy-3,3-dimethylbutyrolactone react almostquantitatively to give panthenol [84].

Alkoxypropylamines react analogously to pri-mary aliphatic amines. They form salts withinorganic or organic acids, and can be convertedto acid amides, sulfonamides, urethanes, andSchiff bases. They can be alkylated with formal-dehyde or formic acid to give dimethylaminocompounds. 3-Methoxypropylamine catalyzesthe addition of hydrogen cyanide to vinyl estersto give 1-cyanoethyl esters [85]. 3-Methoxypro-pylsulfanilylurea obtained from the 3-methoxy-propylammonium salt of N,N-di(acetylsulfani-lyl)urea is an oral antidiabetic agent [86].

5.2. Production

Industrially, N-alkylated isopropanolamines areprepared primarily from amines and propylene


Table


ofN-alkylatedisopropanolamines

Compound

CASregistry

number

Mr

mp,� C

bp(101.3

kPa),� C

r,(20

� C)

g/cm

3

Cubic

expansion

coefficient,

K�1

Heatof

vapori-

zation

kJ/kg

Specific

heat,kJ

kg�1K�1

Specific

electrical

conductivity,

W�1cm

�1

Viscosity

(20

� C),

mPa�s

n20 D

Surface

tension

(20

� C),

mN/m

Flash

point,

� CIgnition

temperature,

� C

Tem

perature

class

Monomethyliso-propanolamine

[16667-45-1]89.14

12.5

149

0.9062

455.6

4.8

�10�7

1.4340

28.7

(22

� C)

58.7

305

T2

Methyldiisopropanolamine

[4402-30-6]

147.22

�32

226

0.945

329.3

1.4

�10�7

47.3

1.4472

(25

� C)

31.0

(22

� C)

110.5

300

T3

Dim

ethylisopropanolamine

[108-16-7]

103.17

�85*

125.8

0.849–

0.852

7.0

�10�4

393.6

2.45

(25

� C)

2�

10�6

1.5

1.4189

24.5

(25

� C)

26

225

T3

Diethylisopropanolamine

131.22

157.5

–

159

0.8570

1.4265

Dibutylisopropanolamine

187.33

�80*

229.1

0.8419

7.8

�10�4

246.6

3.5

1.4361

205

Cyclohexylisopropanolamine

157.26

45.1

238

0.9365

(40

� C)

329.3

2.47

(60

� C)

9.0

�10�4

11.5

(60

� C)

1.4732

111

270

T3

Cyclohexyldiisopropanolamine

215.34

2.0

Cyclooctylisopropanolamine

185.31

�12.85*

275

0.953

7.6

�10�4

234.5

2.24

(20

� C)

5.1

�10�4

665

1.4902

37.0

(20.3

� C)

141

245

T3

Cyclooctyldiisopropanolamine

243.39

29.6

318

0.977

7.4

�10�4

233.95

1.98

(20

� C)

5.7

�10�11

10870

1.4890

38.0

(20.3

� C)

176

245

T3

Aminoethylisopropanolamine

[123-84-2]

119.19

�38*

0.9868

145

1.4750

123

345

T2

1-(2-H

ydroxypropyl)

piperazine

144.22

�17*

1.0108

423

1.4910

115

290

T3

1,4-Bis(2-hydroxypropyl)

piperazine

202.30

97–98

157

250

T3

4-(2-H

ydroxypropyl)

morpholine(12)

145.21

�47*

218

1.0163

314.3

1.92

11.0

1.4642

34.5

92

215

T3

N,N,N

0 N0 -T

etrakis

(2-hydroxypropyl)

ethylenediamine

292.43

þ11*

190

(133Pa)

1.03

(25

� C)

6.7

�10�4

2.297

(50

� C)

2.4

�10�4

45

(100

� C)

1.478

(25

� C)

35.1

201

285

T3

*Pourpoint.


oxide according to the following reactions [67],[87]:

N-Alkylated 1-amino-2-propanols are formedpredominantly [66], [88], [89]. The isomeric 2-amino-1-propanols are obtained only as bypro-ducts (0.2 – 5%, depending on the nature of theamino component). The reactions are carried outat 80 – 160 �C and pressures up to 5 MPa,batchwise or continuously. A detailed descrip-tion can be found in Section 4.2. As in ethanol-amine production, the oxidemust be added to theamine, not vice versa (see Section 2.2). Thecrude reaction products are purified by continu-ous or batchwise distillation.

3-Amino-1-propanol is obtained by hydroge-nating ethylene cyanohydrin. N-Methylated 3-amino-1-propanols are prepared from 3-amino-1-propanol and formaldehyde, with subsequenthydrogenation of the adducts [90]. 3-Alkoxypro-pylamines are prepared from acrylonitrile byaddition to alcohols and subsequent hydrogena-tion [91].


Table 11 gives the specifications for commercialN-alkylated propanolamines and 3-alkoxypropy-lamines. Purity is generally determined by gaschromatography.

5.4. Uses and Economic Aspects

N-Alkylated propanolamines and 3-alkoxypro-pylamines are used mainly as intermediates,especially in the preparation of crop-protectionagents and pharmaceuticals. 3-Alkoxypropyla-T

able


of3-amino-1-propanolsand3-alkoxypropylamines

Compound

CASregistry

number

Mr

mp,� C

bp

(101.3

kPa),� C

r,(20

� C)

g/cm

3

Cubic

expansion

coefficient,K�1

Heatof

vaporization,

kJ/kg

Specificheat,

kJkg�1K�1

Viscosity,

mPa�s

n20 D

Flash

point

� CIgnition

temperature,

� C

Tem

perature

class

3-A

mino-1-propanol

[156-87-6]

75.11

11.5

189

0.98–0.99

8.3

�10�4

641

2.71

36(20

� C)

1.460–1.462

98–100

385

T2

3-D

imethyl-am

ino-1-

propanol

[3179-63-3]

103.17

�32.7

162–163

0.882–0.885

57

3-M

ethoxy-propylamine

[5332-73-0]

89.14

<�7

0118

0.8729

1.2

�10�3

422.9

0.9

(25

� C)

1.4159(25

� C)

27

270

T3

3-Ethoxy-propylamine

[6291-85-6]

103.17

<�7

0134.7

0.861

33.7

245

T3

3-(2-Ethylhexyloxy)-

propylamine

[5397-31-9]

187.33

<�7

0237

0.8466

258.85

2.27

104

220

T3


mines have considerable commercial importancein the preparation of dyes. N-Alkylated propa-nolamines and their derivatives have been em-ployed, in the form of soaps, as lubricating oiladditives, mold release agents [92], [93], textilefinishes, and coatings for paper and wood [94].The propanolammonium salts of alkylarylsulfo-nic acids are used as cleansing boosters anddegreasing agents [95]. 3-Alkoxypropylaminesare utilized as catalysts in the production ofpolyurethane foams and epoxy resins.

3-Alkoxypropylamines and N-alkylpropano-lamines are used as corrosion inhibitors and in thepreparation of aqueous polymer solutions[96–100]. Anion exchangers can be prepared byreacting cellulose with dimethylisopropanola-mine and epichlorohydrin [101].

World demand for N-alkylpropanolaminesand 3-alkoxypropylamines is estimated at5000 t/a. More than 100 t/a of 3-methoxypropy-lamine and dimethylisopropanolamine are used.

6. Storage and Transportation

Alkanolamines should be stored in stainless steelcontainers with exclusion of air (O2, CO2) andmoisture, preferably under dry nitrogen. Storagetemperature should not exceed 40 �C (50 �C forethanolamines). Steel tanks may be used if ab-sorption of iron (up to 10 ppm) is not important.Alkanolamines turn yellow on prolonged stor-age, especially in the presence of oxygen.

Depending on quality requirements and sen-sitivity of the products, steel, stainless steel, orpolyethylene containers can be used for trans-portation. The containers must possess airtight

closures to prevent absorption of water and car-bon dioxide. Zinc and other nonferrous metalsare attacked by alkanolamines. For transporta-tion, particular national regulations, such asGGVS in Germany, should be observed [102].

Rubber gloves and safety goggles should beworn when handling alkanolamines. In somecases, especially with 3-alkoxypropylamines, afull face shield and rubber clothing are advisable.

For safety data of alkanolamines, see thesections on physical properties.

7. Environmental Protection

Ammonia- or amine-containing off-gases fromalkanolamine production are either burned orpurified by acid scrubbing. Very low amineconcentrations (10�3 ppm) can be determinedby modern analytical methods [103].

Wastewater from plant cleaning and acidscrubbing is treated in a sewage plant. Whenproperly fed into a biological treatment plant,alkanolamines are readily degraded by appropri-ate bacteria.

Spilled product should be removed with anabsorptive material such as urea resin foam(Hygromull) or peat dust,which is then incinerated.

8. Toxicology and OccupationalHealth

8.1. General Aspects

All alkanolamines considered here are compiledin Table 12 along with available data on acute

Table 11. Specifications for commercial N-alkylated propanolamines and 3-alkoxypropylamines

Compound Purity, % r (20 �C, DIN51 757), g/cm3

Boiling range

5 – 95 mL (DIN 51

751, DIN 53 406), �C

Color

(DIN-ISO

6271), APHA

Water content

(DIN 51 777), %

Monomethylisopropanolamine 98 0.906 146 – 152 � 50

Methyldiisopropanolamine 98 0.954 226 – 230 � 50

Dimethylisopropanolamine > 99.5 0.849 – 0.852 125 – 127 � 50 < 0.2

Aminoethylisopropanolamine � 98 0.9868 232.5 – 235.5 � 20

N,N,N,N0-Tetrakis(2-hydroxy-propyl)ethylenediamine � 99 1.009 – 1.013 20

3-Dimethylamino-1-propanol 99 0.882 – 0.885 162 – 163

3-Methoxypropylamine 99 0.871 – 0.873 117 – 119 20 < 0.2

3-Ethoxypropylamine 99 0.855 – 0.861 130 – 135 5 < 0.2

3-(2-Ethylhexyloxy)propylamine > 99 0.847 – 0.848 233 – 238 � 40 < 0.2


Table

12.Acute

toxicological

dataandoccupational

exposure

limitsofalkanolamines

a

Acute

toxicity

Localirritation

OELd,mL/m

3(m

g/m

3)

Substance

[CASno.]

LD50,g/kg

Ref.

AIH

(rat)b

Ref.

Skin

cEye

Ref.

Ethanolamines

Monoethanolamine

1.5

(o,rt)

[116],

>8h(520ppm)

[116],

[142]

1–5min:c

c[116]

MAK:2(5.1)

[141-43-5]

1.2

–2.5

(o,rt)

[142],

TLV:3(7.5)

1.0

–2.5

(d,rbt)

[104]

Diethylanolamine

ca.1.6

(o,rt)

[116]

>8h(0.37ppm)

[116]

sei;�1

5min:ni

sei

[116]

OEL(N

L):(15I)sk

[111-42-2]

1.7

–2.8

(o,rt)

[142]

[142]

TLV:0.46(2)sk

8.1

–12.2

(d,rbt)

[142],[104]

1471ppm

(vapor/aerosol,2h)

[106]

m/sli

i[142]

Triethanolamine

ca.7.2

(o,rt)

[116]

>8h(0.0047ppm)

[116],

[142]

4h:ni

ni/sli

[116]

OEL(S):(5)

[102-71-6]

8.4

–11.3

(o,rt)

[142]

20h:i

TLV:(5)

>20(d,rbt)

[142]

2-(2-A

minoethoxy)ethanol

ca.3.4

(o,rt)

[116],

>8h

[116]

cse

i[116]

n.e.

[929-06-6]

ca.2.5

(o,rt)

[159],

�3min:ni

sei

[159]

ca.1.3

(d,rbt)

[181],

�1h:se

i

>3(d,rbt)

[159]

4h:c

Alkylalkanolamines

Monomethylethanolamine

1.39–2.34(o,rt)

[114],[116],

[132]

>8h

[114],

[116]

3min:i4h:c

[132],[133],

[116]

n.e.,sk

[109-83-1]

>2(d,rbt)

[116]

sei

[114],[116]

ca.1.9

(d,rbt)

[132]

ca.1.25(d,rbt)

[133]

Ethylethanolamine

1.1

(o,rt)

[116]

>7h

[116]

cse

i[116]

n.e.

[110-73-6]

1.48(o,rt)

[114]

>8h

[114]

3.67(d,rt)

[116]

n-Propylethanolamine

ca.1(o,rt)

[116]

>8h

3min:sli

cn.e.

[16369-21-4]

>0.4

(d,rbt.)

[116]

>2.9

mgL�1(4

h)�

1[116]

1h:c

[116]

n-Butylethanolamine

ca.1(o,rt)

[116]

>8h

[116]

5min:sei/c

c[116]

n.e.

[111-75-1]

Hydroxyethylaniline

2.73(o,rt)

[116]

>8h

[116]

ni

sei

[116]

n.e.

[122-98-5]

2.23(o,rt)

[140]

ii

[140]

0.06(d,rbt)

[140]

Dim

ethylethanolamine

�2(o,rt)

[116],[134]

LC50ca.6mgL�1

(4h)�

1

[132],

[136]

sei/c

sei/c

[116],[135],

[132]

n.e.

[108-01-0]

1.24–1.6

(o,rt)

[135]

1.2

(d,rbt)

[132]

30min

[116]

1.7

–2.4

(d,rbt)

[135]

Diethylethanolamine

1.33(o,rt)

[116],[113]

>1h

[116]

1h:c

c[116]

MAK:10(50)sk

[100-37-8]

ca.0.89(d,gp)

[113]

TLV:2(9.6)

Dibutylethanolamine

ca.0.6

(o,rt)

[116]

>7h

[116]

>5min:i

sei

[116]

OEL(N

L):(14)sk

[102-81-8]

1.68(d,rbt)

TLV:0.5

(3.5)sk

N-H

ydroxyethylpiperazine

ca.4.2

(o,rt)

[116]

>8h

[116]

sei

sei

[116]

n.e.

[103-76-4]

>5(d,rbt)

[166]


N-H

ydroxyethylm

orpholine

ca.6.8

(o,rt)

[116]

>8h

[116]

ni

sli

[116]

n.e.

[622-40-2]

>16(d,rbt)

[141]

ni

ni

[141]

N-H

ydroxyethylpiperidine

ca.1.1

(o,rt)

[116]

>8h

[116]

c(>

3min)

c[116]

n.e.

[3040-44-6]

1–2(d,rbt)

[116]

Methyldiethanolamine

ca.4.7

(o,rt)

[116],[114]

>8h

[116],[114]

ni

i[116],[114]

n.e.

[105-59-9]

1.95(o,rt)

[132]

>5(d,rbt)

[132],[114]

mi

[132]

n-Butyldiethanolamine

0.6

–1.0

g/kg(o,rt)

[116]

>8h

[116]

15min:sli

cn.e.

[102-79-4]

20h:c

[116]

Propanolamines

andIsopropanolamines

Monoisopropanolamine

4.26(o,rt)

[104]

>8h

[116]

15min:c

c[116]

n.e.

[78-96-6]

2.7

(o,rt)

[116]

4h(1-%

sol.):

[138]

[6168-72-5]e

1.64(d,rbt)

[105]

ni

2.7

(o,rt)

[116]

mi

sei

[104],[105]

Diisopropanolamine

6.72(o,rt)

[104]

>8h

[116]

sei

sei

[104]

n.e.

[110-97-4]

6(o,rt)

[116]

15min:ni

mi

[116]

20h:m

i[116]

Triisopropanolamine

6.5

(o,rt)

[104]

>8h

[116]

sei

[104],[105]

n.e.

[122-20-3]

>10(d,rbt)

[105]

2h(vapors,

170

� C)

[137]

4(o,rt)

[116]

15min:ni

sei

20h:sli

mi

[116]

3-A

mino-1-propanol

2.83(o,rt)

[104],[105]

>8h

sei

[104],[105]

n.e.

[156-87-6]

1.3

(o,rt)

5min:se

ic

>2(d,rt)

[116]

LC50>

16.4

mgL�1h�1

[116]

15min:c

[116]

AlkylatedPropanolamines/Isopropanolamines

3-D

imethylamino-1-propanol

1.86(o,rt)

[116]

8h

[116]

15min:se

i/c

sei/c

[116]

n.e.

[3179-63-3]

Monomethylisopropanolamine

1(o,rt)

[116]

>7h

[116]

15min:c

c[116]

n.e.

[16667-45-1]

Dim

ethylisopropanolamine

1.36(o,rt)

[116]

10min

[116]

5min:c

c[116]

n.e.

[108-16-7]

1.89(o,rt)

[104]

Methyldiisopropanolamine

2.15–3.83(o,rt)

[116]

n.e.

[4402-30-6]

3-A

lkoxypropylamines

3-M

ethoxypropylamine

6.26(o,rt,aq,sol.,pH

7)

[116]

1h

[116]

5min:c

c[116]

n.e.

[5332-73-0]

0.63(o,rt)

[139]

3-Ethoxypropylamine

1.1

–1.5

(o,rt)

[116]

1h

[116]

1min:c

c[116]

n.e.

[6291-85-6]

3-(2-Ethylhexyloxy)propylamine

0.85(o,rt)

[116]

8h

[116]

5min:c

c[116]

n.e.

[5397-31-9]

0.32(o,rt)

0.36(d,rbt)

[104]

aSymbols:o¼

oral;d¼

dermal;rt¼

rat;rbt¼

rabbit;gp¼

guinea

pig;i¼

irritating(n

¼not,sl¼

slightly,m

¼moderately,se

¼severely);c¼

corrosive.

bAIH

¼acuteinhalationhazard:ratsinhalean

atmosphereenriched

withvaporat20

� C(w

hen

nototherwiseindicated,vapor-saturatedair);time¼

durationofexposure

required

tocause

thefirstdeath.

cTheskin

irritationforthespecifictimeofexposure

tothesubstance

isgiven.

dOEL¼

occupational

exposure

limit:MAK

(Germany,1999),TLV

(USA,1997);NL¼

TheNetherlands,S¼

Sweden;I¼

inhalable

(totalaerosol),sk

¼skin;n.e.¼

notestablished.

eMonoisopropanolamine(d,l)[78-96-6]contains2-amino-1-propanol(d,l)[6168-72-3].


toxicity, irritant/caustic properties, and occupa-tional exposure limits.

Most prominent among the toxic effects ofalkanolamines is their caustic/irritant action onexposed skin and mucous membranes. Thiseffect decreases from primary to tertiary alka-nolamines and is distinctly less pronounced orabsent in their salts due to compensation ofalkalinity. An increase in the number of hy-droxyl groups further alleviates the irritantproperties.

The low vapor pressure of these compounds atroom temperature explains the generally lowacute inhalation hazard.However, vapors formedat elevated temperatures may irritate eyes andrespiratory tract. Aqueous solutions containing1 – 10% of monoalkanolamines such as mono-ethanol- and monoisopropanolamine are stillirritating to eyes and skin. In principal, this alsoapplies to the N-dialkanol derivatives, albeit to alesser degree. Available data suggest that alka-nolamines can penetrate the skin.

In general, the acute toxicity of the testedcompounds is moderate to low and nonspecific;it is probably dominated by local irritant effectsowing to their alkalinity. In a few cases, acute orlong-term systemic symptoms may involveneuropharmacological effects that interact withacetylcholine synthesis and neurotransmitterfunction or neurotoxicity as a consequence ofdisturbed neural membrane structure.

The mutagenic potential of alkanolamines isvery low. However, in the presence of nitrite orunder other appropriate conditions, primary andsecondary alkanolamines form nitroso com-pounds which may be mutagenic or carcinogen-ic. Existing regulatory limitations on the use ofcompounds need to be considered as well aswork-place regulations.

The skin-sensitizing potential of alkanola-mines is very low.

8.2. Ethanolamines

The chemistry, biochemistry, and toxicity ofmonoethanolamine (MEA), diethanolamine(DEA), and triethanolamine (TEA) have com-prehensively been reviewed [142]. MEA is anatural building block of a group of importantmembrane components, the phospholipids, andthe precursor in the de-novo synthesis of choline

to form lecithin. DEA interferes with the MEAand phospholipid metabolism by replacing cho-line. The accumulation of atypical phospholipidsappears to be the determinant in the systemictoxicity of DEA. TEA does not exhibit theseproperties.

There is no evidence that MEA and DEAhave a sensitizing potential [142], while forTEA, occasional cases of allergic contactdermatitis were reported [108], [109]; however,no sensitizing effect was found in guineapigs [110], [164], [142].

The majority of genotoxicity tests, includingbacterial and mammalian in vitro test systems,indicate the absence of mutagenic activity inthese ethanolamines [142].

Monoethanolamine. Early inhalation stud-ies with various animal species demonstrated thatthe extreme irritancy of an MEA atmosphere toexposed skin and the respiratory tract resulted inpronounced discomfort and behavioral depressionalready at concentrations of 5 – 15 ppm (ca.12.5 – 38 mg/m3) [142]. Nonstop inhalation forabout 3 – 6 weeks of 66 – 75 ppm MEA vaporswas lethal to guinea pigs and rats; 100 ppm waslethal to dogs. The liver and the kidney wereidentified as target organs at high doses [142].Oral administration of 1.28 g kg�1 d�1 in the feedto rats for 30 – 90 d was lethal, whereas a dose of0.64 g kg�1 d�1 led to changes in the liver andkidney weights; a dose of 0.32 g kg�1 d�1 wastolerated without any toxic effects [105], [142].

MEA produced no signs of developmentaltoxicity in standard developmental toxicity testswhen applied orally to pregnant rats [142], [143]and dermally to pregnant rabbits [144]. Thisrefutes the putative increases in the incidence offetal malformations, unrelated to dose, in a pre-vious nonstandard study [142].

Diethanolamine. All toxicity data for re-peated exposure suggest that DEA can be incor-porated in cell membranes and affects their sta-bility [142]. The liver and kidneys are the majortarget organs, but demyelinization of nerve fibersand anemia, presumably due to altered composi-tion of the erythrocyte membranes, is also possi-ble. Toxic effects were observed after continuousinhalation of 25 ppm for 9 d or 6 ppm for13 weeks (5 d/week), which was lethal to someof the exposed rats, and after a seven-week


administration to rats of neutralized diethanola-mine at a concentration of 4 mg/mL in drinkingwater [107], [142]. Oral administration of 0.02 gkg�1 d�1 to rats for 90 d was tolerated withoutany signs of toxicity, whereas a dose of 0.09 gkg�1 caused an increase in liver and kidneyweights. A dose of 170 mg kg�1 d�1 was lethal[105], [142]. A subchronic no observed adverseeffect level was established at a dose of 20 –25 mg kg�1 d�1 for oral exposure in rats [145].

In two-year dermal carcinogenicity studies,increased incidence of liver tumors was observedinmice, but not in rats [146]. Follow-up studies intwo transgenicmouse lines, whichwere expectedto exhibit enhanced sensitivity to carcinogenicsubstances, clearly failed to elicit any carcino-genic potential of DEA [147]. Furthermore, thedevelopment of DEA-related neoplasia in mouseliver could reasonably be explained by a non-genotoxic mechanism expressed by disruption ofcholine metabolism [148].

DEA was maternally toxic and fetotoxic (i.e.,retarded ossification) at oral doses of 0.2 g kg�1

d�1 [142], [149], and at dermal doses of 1.5 and0.35 g kg�1 d�1 in rats and rabbits, respectively,but failed to produce structural malformations inany test [142].

Triethanolamine has a low systemic toxic-ity, mainly restricted to the kidney as targetorgan [112], [142]. In contrast to DEA it isreadily eliminated via the urine without under-going appreciable metabolism. Extensive muta-genicity testing did not reveal a genotoxic effect[154], [154]. In subacute inhalation studies withrats and mice exposed to TEA aerosols over a16-d period (0.125 – 2 g/m3, 6 h/d, 5 d perweek), onlyminimal to slight acute inflammationof the submucosa of the larynx but no effects onnasal or lung tissue were noted; this indicates alack of severe irritation from TEA exposure[153], [153]. Oral administration of 0.08 g kg�1

d�1 to rats in the feed for 90 d was toleratedwithout toxic effects. A dose of 0.17 g kg�1 d�1

caused changes in the liver and kidney weights,while 0.73 g kg�1 d�1 led to histopathologicalchanges in both organs and deaths [181], [105].High doses of ca. 1.4 g kg�1 d�1 administered inthe drinking water for 14 d produced no signifi-cant signs of intoxication in rats and mice [142].Two-year exposure to doses above 0.5 g kg�1

d�1 in the drinkingwater led to an acceleration of

the chronic, age-related nephropathy usuallyobserved in this rat strain [112], [142], whilethere were no morphological effects in miceunder comparable conditions [150], [142]. Noconclusions about apparently positive oncogenicfindings can be drawn from another nonverifiablelifelong feeding study in mice [111], [142].

A dermal carcinogenicity study in mice sug-gested a significant increase in the spontaneoustumor rate of hepatocellular adenomas in the high-dosemale and female groups (2 and 1 g kg�1 d�1,respectively). However, because of an infection ofthe animals withHelicobacter hepaticus, the studycould not be evaluated andwas abandoned asbeinginadequate [165]. There was no significant carci-nogenicity in rats epicutaneously administeredTEA at doses from 30 to 250 mg kg�1 d�1

[165]. However, because of a marginally positivetrend in the incidence of renal tubular adenomas inmales, the Peer Review concluded on ‘‘equivocalevidence’’ in male rats [165].

2-(2-Aminoethoxy)ethanol (diglycolamine)applied as 10% ethanolic solution showed noskin-sensitizing activity in the Buehler test[159], [167]. The Ames test [143], [159] and aDNA repair assay in rat hepatocytes failed toindicate a genotoxic potential [159]. A cell trans-formation study using mouse BALB/3T3 cellswas also negative [159].

8.3. N-Alkyl- undN-Arylethanolamines

Methylethanolamine was not mutagenic inthe Ames test [169]. Continuous inhalation ex-posure to 1.8 and 9.7 ppm (ca. 0.006 and 0.03 gm�3, respectively) for 90 d resulted in localirritation (inflammatory effects on the nasal epi-thelium), but no treatment-related systemicallytoxic findings in rats and guinea pigs. In maledogs, dose-related atrophic degenerations in thetestes were noted under comparable test condi-tions [151]. After 32-d administration of 0.004,0.04, and 0.4 g kg�1 d�1 in the diet to rats,relative liver weights were increased in all dosegroups with slight hepatic vacuolization at thetwo upper levels, and slight testicular edema andatrophy in the high-dose male group [151]. Therewas no evidence of embryotoxic and teratogeniceffects on fetuses after inhalation exposure to150 ppm (ca 0.47 g/m3) in pregnant rats [152].


Ethylethanolamine is reported to be nega-tive in the Ames test [155]. After ingestion indrinking water for 30 d, mainly dose-relatedhistopathological changes in the kidneys devel-oped in rats, with diffuse edema in the tubularepithelia at about 0.023 g kg�1 d�1 and progres-sive degenerative lesions at higher doses; fur-thermore, counts of white and red blood cellswere enhanced [156]. After 90-d administration,the above-mentioned effects appeared to be lesspronounced at corresponding dosage [156].

In a specially designed test, ethylethanola-mine applied at an oral dose of about 0.18 g kg�1

d�1 during the implantation period (day 1through 6 of gestation), produced implantationlosses of some 50% in pregnant rats [157].

n-Propylethanolamine was nonmutagenicin the Salmonella typh./E. coli reverse mutationtest [158].

n-Butylethanolamine was nonmutagenicin the Salmonella typh./E. coli reverse mutationtest [158].

Hydroxyethylaniline was nonsensitizing inthe guinea pig maximization test [143] and wasmutagenic in a bacterial assay using only Salmo-nella typh. TA 98 [143]. Methemoglobinemiadeveloped in cats after oral and dermal exposure(54.5 and 545 mg kg�1, respectively), a knowneffect of aromatic amines [116].

Dimethylethanolamine occurs as interme-diate in endogenous choline synthesis andtherefore interferes with phospholipid and ace-tylcholine metabolism. It is said to have somestimulatory effect on the CNS by influencingneurotransmitter activity [163]. No skin sensiti-zation was induced in guinea pigs [160]. A broadspectrum of various genotoxicity assays, includ-ing bacteria [135], [169],mammalian cells [135],[161] and an in-vivo micronucleus test in mice[135], [161] gave no evidence of mutagenicpotential.

Inhalation toxicity is associated with stronglocal irritation in the nasal region and the eyes; nopathological changes of inner organs occurred inrats exposed to concentrations of 98 ppm (ca.0.36 g/m3) for two weeks. Thymus atrophy wasseen at 288 ppm (ca. 1 g/m3), but no histologicallesions of the central or peripheral nervous sys-

tem [136]. At 24 ppm (ca. 0.08 g/m3) over 13weeks, no systemic toxicity was noted, and tran-sient corneal opacity was observed as a localadverse effect [136].

Following the administration of 0.2 – 0.3 gkg�1 d�1 in drinking water for more than 100weeks, no increase in tumor incidence was ob-served in mice in a special test model using twomice strains infected with mammary-tumor pro-virus [162].

There was no evidence of developmental ef-fects on fetuses after inhalation exposure to ma-ternally toxic concentrations (up to 100 ppm or0.48 g/m3) during pregnancy of rats [135], [161].

Diethylethanolamine is also a metaboliteof the local anesthetic procaine and has somepharmacological activity (vasodilatation, de-pression of nerve conductivity). No skin sensiti-zation was induced in guinea pigs [168], and nomutagenicity in Ames tests [143], [169]. Inhala-tion toxicity is associated with strong local irri-tation of the nasal region and extreme discomfortof the exposed animals; no pathological changesof inner organs occurred in rats exposed to con-centrations of up to 76 ppm (0.37 g/m3) for 14weeks [170], [171]. Likewise, there were nosignificant treatment-related findings in rats thatreceived ca. 0.013 and 0.033 g kg�1 d�1 andsuccessively increased doses of up to 0.67 gkg�1 d�1 in the diet for two years [172]. Markedneurological action was observed in dogs atrepeated dietary doses of ca. 0.04 g kg�1 d�1

and above, expressed as tremor and head shakingfollowed by ataxia and convulsions at elevateddoses [172]. There was no evidence of develop-mental effects on fetuses after inhalative expo-sure to maternally toxic concentrations (up to100 ppm or 0.48 g/m3) during pregnancy of rats[173].

Dibutylethanolamine. Five-week adminis-tration of neutralized dibutylethanolamine indrinking water in doses of 0.43, 0.20, and 0.13 gkg�1 d�1 (male rats) and 0.33, 0.24, and 0.14 gkg�1 d�1 (female rats) produced no substance-related, histopathological effects; the lowest dosewas devoid of any macroscopic findings [115].Irritation of the eyes and nose was observed afterinhalative exposure of rats (70 ppm or ca. 0.5 gkg�1 d�1, 5 d per week, 6 h/d). This exposurewas lethal to one of five animals and led to an


increase in the relative liver and kidney weightsand to liver damage. A concentration of 22 ppm(ca. 0.16 g kg�1 d�1) for 6 h/d over a period ofsix months was tolerated by rats without anysigns of toxicity [115].

Hydroxyethylpiperazine and Hydroxy-ethylmorpholine. Hydroxyethylpiperazine[175] and hydroxyethylmorpholine [176] werenonmutagenic in an Ames test. But the lattersubstance is reported to exhibit some genotoxicactivity by inducing DNA damage and repair inrat liver cells and cell transformation in culturedmouse embryo fibroblasts [176].

N-Hydroxyethylpiperidine (2-piperidino-ethanol) was not mutagenic in an Ames test withSalmonella typh. TA100, TA98, and E. coliWP2[177] and in a cytogenetic assay using Chinesehamster cells [178].

Methyldiethanolamine is reported to benonsensitizing in a guinea pig maximization test[174] and proved to be nonmutagenic in variousgenotoxicity assays, including bacterial [161],[169] and mammalian cells and an in vivo micro-nucleus test [161]. After prolonged dermal ad-ministration to rats, no systemic effects werefound up to the top dose of 0.75 g kg�1 d�1; butlocal changes at the treated site, characterized asacanthosis and hyperkeratosis, were induced atdoses of 0.25 g kg�1 d�1 and higher. No patho-logical changes were noted at 0.1 g kg�1 d�1

[174].

n-Butyldiethanolamine was nonmutagenicin the Salmonella typh./E. coli reverse mutationtest [158].

8.4. Propanolamines

Monoisopropanolamine induced no skin-allergic and photoallergic reactions in 150 hu-mans tested in a repeated insult patch test [179].Negative mutagenic results were obtained inAmes tests using Salmonella and E. coli testerstrains [180], [169]. The ninefold inhalation of upto 0.24 g/m3 (5 d/week, 6 h/d) failed to produceclinical signs of intoxication or macroscopicchanges in rats and mice [179]. Likewise, after90-d feeding of 0.14 to 2.2 g kg�1 d�1 to rats, no

effects were reported, but weight changes of theliver and kidney occurred at high dosage [181].No increase in tumor incidences occurred in ratsthat received 1% in the feed (ca. 0.67 g kg�1

d�1) for 94weeks. However, in combinationwith0.3% sodium nitrite in drinking water, endoge-nously produced nitroso compounds inducedtumors [182].

Diisopropanolamine applied as 2% aque-ous solution induced no skin-allergic and photo-allergic reactions in a repeated insult patch testwith 25 volunteers [179]. One case report ofcontact allergy has been published [183]. Der-matological testing programs using 1% diiso-propanolamine in facial sunscreen resulted intwo positively responding subjects out of tworandom collectives of 424 volunteers in total[179]. Based on a nonverifiable test report, aweakly allergic potential was concluded in guin-ea pigs [184]. The substance was nonmutagenicin the Ames test and induced no chromosomalaberrations in rat lymphocytes [185], [186].When it was administered to rats at doses of0.1 – 3 g kg�1 d�1 in the drinking water for2 weeks, no symptoms were observed up to 0.6 gkg�1 d�1. The dose of 3 g kg�1 d�1 was lethal totwo out of five male animals; the prominenteffects for this dose group included a significantloss in body and organ weight, acute inflamma-tion and degeneration of kidneys and urinarybladder, and general liver atrophy [138]. Afterfour weeks of dermal exposure to up to 0.75 gkg�1 d�1, no pathological changes were noted inrats, except for skin irritation at the treated site at0.5 g kg�1 d�1 and higher [186]. No clinical andorganotoxic findings, as well as no increase intumor incidences, were reported in rats that re-ceived 1% in the feed (ca. 0.5 g kg�1 d�1) for 94weeks. However, in combination with sodiumnitrite in drinking water, endogenously producednitroso compounds induced tumors [187].

Triisopropanolamine is reported to be non-sensitizing in humans when patch-tested as a1.1% additive in a cosmetic lotion [179] and assuch in a guinea pig maximization test [184]. Itwas nonmutagenic in the Ames test [169] andfailed to induce chromosomal aberrations in amouse micronucleus assay [143]. When it wasadministered to rats at doses of 0.1 to 0.2 g kg�1

d�1 in drinking water for two weeks, no effects


were observed at 0.1 and 0.33 g kg�1 d�1, withminor, but noncharacteristic findings at the high-er doses [138]. No evidence of a fetotoxic andteratogenic potential was found in the progenyfrompregnant rats exposed to oral doses reachingmaternal toxicity [137], [143].

Propanolamine (3-amino-1-propanol)showed no skin-sensitizing potential in an earlyepicutaneous nonstandard test with guinea pigs[188] and no mutagenic activity in the Ames test[143], as well as in an SCE assay with CHO cells[189]. In a screening test, oral treatment of rats andcats with about 0.78 g kg�1 d�1 in 4 and 5%aqueous solutions for twoweeks (10 applications)caused no significant macroscopic and histologi-cal abnormalities [188].

3-Methoxypropylamine caused skin sensi-tization in the Buehler test (5%in ethanol) [139].There was no evidence of mutagenic activity inthe Ames test [139], [143], two unspecified as-says, a UDS assay, and amicronucleus test [139].

3-(2-Ethylhexyloxy)propylamine was re-ported to be nonmutagenic in the Ames test [19].

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Further Reading

A. C. Eachus, A. F. Bollmeier: Alkanolamines from Nitro

Alcohols, ‘‘Kirk Othmer Encyclopedia of Chemical Tech-

nology’’, 5th edition, John Wiley & Sons, Hoboken, NJ,

online DOI: 10.1002/0471238961.0112110102151212.

a01.pub2.

C. Jones, M. R. Edens, J. F. Lochary: Alkanolamines from Olefin

Oxides andAmmonia, ‘‘KirkOthmerEncyclopedia ofChem-

ical Technology’’, 5th edition, JohnWiley& Sons, Hoboken,

NJ, online DOI: 10.1002/0471238961.0112110105040514.

a01. pub2.


Documents

"Ethanolamines and Propanolamines," in: Ullmann's Encyclopedia