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Article No : a10_101

Ethylene Glycol
SIEGFRIED REBSDAT, Hoechst Aktiengesellschaft, Gendorf, Federal Republic
of Germany
DIETER MAYER, Hoechst Aktiengesellschaft, Frankfurt, Federal Republic of Germany

1.
2.
3.
4.
4.1.
4.1.1.
4.1.2.
4.2.
4.2.1.
4.2.2.
5.
6.

Introduction. . . . . . . . . . . . . . . . . . . . . . .
Physical Properties . . . . . . . . . . . . . . . . .
Chemical Properties . . . . . . . . . . . . . . . .
Production . . . . . . . . . . . . . . . . . . . . . . . .
Ethylene Oxide Hydrolysis. . . . . . . . . . . .
Current Production Method . . . . . . . . . . . .
Possible Developments . . . . . . . . . . . . . . .
Alternative Methods of Ethylene Glycol
Production . . . . . . . . . . . . . . . . . . . . . . . .
Direct Oxidation of Ethylene . . . . . . . . . . .
Synthesis from C1 Units. . . . . . . . . . . . . . .
Environmental Protection and Ecology . .
Quality Specifications and Analysis . . . . .

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7.
8.
8.1.
8.2.
9.
10.
11.
11.1.
11.2.

Storage and Transportation. . . . . . . . . . . .


Derivatives . . . . . . . . . . . . . . . . . . . . . . . . .
Di-, Tri-, Tetra-, and Polyethylene Glycols
Ethers and Esters. . . . . . . . . . . . . . . . . . . .
Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Economic Aspects . . . . . . . . . . . . . . . . . . .
Toxicology and Occupational Health . . . . .
Ethylene Glycol . . . . . . . . . . . . . . . . . . . . .
Ethylene Glycol Derivatives. . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . .

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1. Introduction

2. Physical Properties

Ethylene glycol [107-21-1,] 1,2-ethanediol,


HOCH2CH2OH, Mr62.07, usually called glycol,
is the simplest diol. It was first prepared by
WURTZ in 1859 [1]; treatment of 1,2-dibromoethane [106-93-4] with silver acetate yielded
ethylene glycol diacetate, which was then hydrolyzed to ethylene glycol.
Ethylene glycol was first used industrially in
place of glycerol during World War I as an
intermediate for explosives (ethylene glycol
dinitrate) [2], but has since developed into a
major industrial product.
The worldwide capacity for the production of
ethylene glycol via the hydrolysis of ethylene
oxide [75-21-8] (! Ethylene Oxide) is estimated to be ca. 7x106 t/a.
Ethylene glycol is used mainly as an antifreeze in automobile radiators (! Antifreezes)
and as a raw material for the manufacture of
polyester fibers (! Fibers, 4. Synthetic Organic;
! Polyesters).

Ethylene glycol is a clear, colorless, odorless


liquid with a sweet taste. It is hygroscopic and
completely miscible with many polar solvents,
such as water, alcohols, glycol ethers, and
acetone. Its solubility is low, however, in nonpolar solvents, such as benzene, toluene, dichloroethane, and chloroform. The UV, IR, NMR,
and Raman spectra of ethylene glycol are given
in [3]. Following are some of the physical properties of ethylene glycol [46]:

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


DOI: 10.1002/14356007.a10_101

bp at 101.3 kPa
fp
Density at 20  C
Refractive index, n20
D
Heat of vaporization at 101.3 kPa
Heat of combustion
Critical data
Temperature
Pressure
Volume

197.60  C
13.00  C
1.1135 g/cm3
1.4318
52.24 kJ/mol
19.07 MJ/kg
372  C
6515.73 kPa
0.186 L/mol

532

Ethylene Glycol

Flash point
Ignition temperature
Lower explosive limit
Upper explosive limit
Viscosity at 20  C
Cubic expansion coefficient at 20  C

Vol. 13


111 C
410  C
3.20 vol %
53 vol %
19.83 mPa  s
0.62103 K1

Ethylene glycol is difficult to crystallize;


when cooled, it forms a highly viscous, supercooled mass that finally solidifies to produce a
glasslike substance.
The widespread use of ethylene glycol as an
antifreeze is based on its ability to lower the
freezing point when mixed with water. The
physical properties of ethylene glycol water
mixtures are, therefore, extremely important.
The freezing points of mixtures of water with
monoethylene glycol and diethylene glycol
[111-46-6] are shown in Figure 1. The temperature dependencies of the thermal conductivity,
density, and viscosity of ethylene glycol and
ethylene glycol water mixtures are shown in
Figures 23, and 4 respectively [7]. The Prandtl
numbers (the ratio of the viscosity to the thermal
conductivity) derived from these values are
given in Figure 5 [7]. The vapor pressures of
ethylene glycol water mixtures have been
obtained from [8] by interpolation and are listed
in Table 1.

3. Chemical Properties
Ethylene glycol, like other alcohols, undergoes
the reactions typical of its hydroxyl groups,
which are described elsewhere ( ! Alcohols,
Aliphatic). Thus, only the special chemical

Figure 1. Freezing points of mono- and diethylene glycol


water mixtures
a) Monoethylene glycol; b) Diethylene glycol

Figure 2. Temperature dependence of the thermal conductivity of ethylene glycol water mixtures
Ethylene glycol content, mol %: a) 0; b) 25; c) 55;
d) 75; e) 100

characteristics and industrially important reactions of ethylene glycol are considered here. The
two adjacent hydroxyl groups allow cyclization,
and polycondensation; one or both of these
functional groups may, of course, also react to
give other derivatives.
Oxidation. Ethylene glycol is easily
oxidized to form a number of aldehydes and
carboxylic acids by oxygen, nitric acid, and other

Figure 3. Temperature dependence of the density of ethylene


glycol water mixtures
Ethylene glycol content, mol %: a) 0; b) 26.1; c) 50.95;
d) 76.9; e) 100

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Ethylene Glycol

533

Table 1. Vapor pressure of ethylene glycol water mixtures


Water content,
wt %
0
10
20
30
40
50
60
70
80
90
100

Figure 4. Temperature dependence of the viscosity of


ethylene glycol water mixtures
Ethylene glycol content, mol %: a) 0; b) 25; c) 49.90;
d) 74.36; e) 100

Vapor pressure, in kPa at


65.1  C

77.7  C

90.3  C

0.30
6.61
11.30
14.70
17.10
18.81
20.16
21.45
22.98
25.08
28.04

0.52
11.65
19.68
25.45
29.68
32.92
35.58
37.92
40.05
41.91
43.34

1.20
19.73
33.01
42.49
49.37
54.60
58.87
62.60
65.98
68.93
71.10

oxidizing agents. The typical products derived


from the alcoholic functions are glycolaldehyde
(HOCH2CHO) [141-46-8,] glycolic acid
(HOCH2COOH) [79-14-1,] glyoxal (CHOCHO) [107-22-2,] glyoxylic acid (HCOCOOH)
[298-12-4,] oxalic acid (HOOCCOOH) [14462-7,] formaldehyde (HCHO) [50-00-0,] and
formic acid (HCOOH) [64-18-6]. Many of these
compounds are described in separate articles.
Variation of the reaction conditions can lead to
the selective formation of a desired oxidation
product. Gas-phase oxidation with air in the
presence of copper catalysts is of industrial
importance for the production of glyoxal
(! Glyoxal and ! Glyoxylic Acid). Glycol
cleavage occurs in acidic solution with certain
oxidizing agents such as permanganate, periodate, or lead tetraacetate. Cleavage of the C-C
bond mainly produces formaldehyde, some of
which is further oxidized to formic acid [9].
1,3-Dioxolane Formation. 1,3-Dioxolanes
are formed by reacting ethylene glycol with
carbonyl compounds [10]:

Figure 5. Temperature dependence of the Prandtl numbers


of ethylene glycol water mixtures
Ethylene glycol content, mol %: a) 0; b) 20; c) 40; d) 60;
e) 80; f) 100

Acetalization to the cyclic 1,3-dioxolane


proceeds more readily than acetal formation
from straight-chain alcohols. If water is removed
from the reaction mixture, an excellent yield can
be obtained. This reaction is used to protect
carbonyl groups in organic syntheses.

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Ethylene Glycol

1,3-Dioxolanes can also be formed from


ethylene glycol by transacetalization. Examples
are the reactions of ethylene glycol with orthoformates [11]:

or with dialkyl carbonates:

1,4-Dioxane Formation. Ethylene glycol


can be converted to dioxane [123-91-1 ] by
dehydration in the presence of acidic catalysts
[12]:

Ether and Ester Formation. Ethylene glycol can be alkylated or acylated by the customary methods to form ethers or esters, respectively. However, the presence of two hydroxyl
groups leads to the formation of both monoand diethers and mono- and diesters, depending
on the initial concentrations of the individual
reactants. The esterification of ethylene glycol
with terephthalic acid [100-21-0] to form
polyesters is especially important (! Fibers,
4. Synthetic Organic; ! Polyesters).

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industrially since these homologues are formed


as byproducts during the production of ethylene
glycol (cf. Section 4.1.1).

Decomposition with Alkali Hydroxide.


Glycol is a relatively stable compound, but
special care is required when ethylene (or
diethylene) glycol is heated at a higher temperature in the presence of a base such as sodium
hydroxide. Fragmentation of the molecule begins at temperatures above 250  C and is
accompanied by the exothermic evolution of
hydrogen (D H 90 to 160 kJ/kg) [13].
This leads to a buildup of pressure in closed
vessels.

4. Production
Although ethylene glycol has been known since
1859 (WURTZ) [1], it was not produced industrially until World War I. Its synthesis was then
based on the hydrolysis of ethylene oxide [7521-8] produced by the chlorohydrin process
(! Chlorohydrins, Chap. 4.). Production from
formaldehyde [50-00-0] and carbon monoxide
was also used commercially from 1940 to 1963
[14]. Neither of these methods is now used,
however; the older literature should be consulted for details [2, 12]. Direct oxidation of
ethylene [74-85-1] to ethylene glycol was also
employed commercially for a short time [15],
but was abandoned, probably due to problems
caused by corrosion [16].

4.1. Ethylene Oxide Hydrolysis


4.1.1. Current Production Method
Ethoxylation. Ethylene glycol reacts with
ethylene oxide to form di-, tri-, tetra-, and polyethylene glycols. The proportions of these glycols found in the reaction product are determined
by the catalyst system that is used and the glycol
excess. A considerable excess of glycol is required to obtain the lower homologues in a
satisfactory yield. This reaction is rarely used

Only one method is currently used for the industrial production of ethylene glycol. This method
is based on the hydrolysis of ethylene oxide
obtained by direct oxidation of ethylene with air
or oxygen (! Ethylene Oxide). The ethylene
oxide is thermally hydrolyzed to ethylene glycol
without a catalyst. Figure 6 shows a simplified
scheme of a plant producing ethylene glycol
by this method. The ethylene oxide water

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Ethylene Glycol

535

Figure 6. Flow diagram for a glycol plant


a) Reactor; b) Drying column; c) Monoethylene glycol column; d) Diethylene glycol column; e) Triethylene glycol column;
f) Heat exchanger

mixture is preheated to ca. 200  C, whereby the


ethylene oxide is converted to ethylene glycol.
Di-, tri-, tetra-, and polyethylene glycols are also
produced, but with respectively decreasing
yields (see also Chap. 3).
The formation of these higher homologues is
inevitable because ethlyene oxide reacts with
ethylene glycols more quickly than with water;
their yields can, however, be minimized if an
excess of water is used a 20-fold molar excess is
usually employed. Figure 7 shows the composition of the resulting product mixture as a function
of the ratio of water to ethylene oxide. Although
the values were determined by using sulfuric acid
as a catalyst [17], they also apply as a good

approximation for the reaction without a catalyst.


Thus, in practice almost 90 % of the ethylene
oxide can be converted to monoethylene glycol,
the remaining 10 % reacts to form higher homologues:

Figure 7. Composition of the product obtained on hydrolysis


of ethylene oxide (EO) as a function of the water to ethylene
oxide ratio
a) Monoethylene glycol; b) Diethylene glycol; c) Triethylene
glycol; d) Higher poly(ethylene glycols)

4.1.2. Possible Developments

After leaving the reactor, the product mixture is purified by passing it through successive
distillation columns with decreasing pressures.
Water is first removed and returned to the
reactor, the mono-, di-, and triethylene glycols
are then separated by vacuum distillation. The
yield of tetraethylene glycol is too low to
warrant separate isolation. The heat liberated
in the reactor is used to heat the distillation
columns. A side stream must be provided to
prevent the accumulation of secondary products, especially small amounts of aldehydes,
which are produced during hydrolysis. The
shape of the reactor affects the selectivity
of the reaction. Plug-flow reactors are superior
to both agitator-stirred tanks and column
reactors [18].

The glycol production method described in


Section 4.1.1 is the only one of current industrial

536

Ethylene Glycol

importance. It is simple, but has some major


drawbacks:
1. The selectivity of the first step the
production of ethylene oxide is low (ca.
80 %).
2. The selectivity of ethylene oxide hydrolysis is
low ca. 10 % is converted to di- and triethylene glycol.
3. Energy consumption for the distillation of the
large amount of excess water is high.
Therefore, much research has been carried out to
improve this process. The search for better silver
catalysts is an objective for point 1 (! Ethylene
Oxide). Points 2 and 3 must be considered together, since higher selectivity for ethylene oxide
hydrolysis automatically reduces the excess of
water required.
Many catalysts have been described in the
literature that are able to optimize selectivity
or lower the reaction temperature and the
required excess of water. Acids and bases are
known to accelerate the reaction rate. The
kinetics of the acid [19] and base [20] catalysis
of ethylene oxide hydrolysis have been thoroughly investigated; mechanisms are discussed
in [21]. The industrial feasability of catalysis
with ion-exchange columns in the liquid phase
[22, 23] and the gas phase [24] has been tested.
Although the use of catalysts allowed the
reaction temperature to be lowered, selectivity
was not significantly enhanced. Furthermore,
the catalyst needed to be separated and either
fed back into the reaction mixture or replaced.
As a result of these disadvantages, these types
of catalysis have not proved to be of commercial use. However, catalysts that improve
selectivity have been described in patents; they
include molybdates [25], vanadates [26], ion
exchangers [27], and organic antimony compounds [28]. However, their advantages do not
yet seem to justify their use on an industrial
scale.
The selective synthesis of ethylene glycol via
the intermediate ethylene carbonate (1,3-dioxolan-2-one) [96-49-1] seems to be a promising
alternative. This compound is obtained in high
yield (98 %) by reacting ethylene oxide with
carbon dioxide and can be selectively hydrolyzed
to give a high yield of ethylene glycol. Only

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double the molar quantity of water is required for


this reaction.

According to a Halcon patent, ethylene oxide can be extracted from the aqueous solution,
formed during its production, with supercritical carbon dioxide [29]. An ethylene oxide
carbon dioxide solution is obtained, which
reacts to form ethylene carbonate. Hydrolysis
of the ethylene carbonate then yields ethylene
glycol. Possible catalysts for this reaction are
quaternary ammonium and phosphonium salts,
such as R4NHal, R4PHal, or Ph3PCH3I. Problems such as product separation and catalyst
feedback still need to be resolved, but this
method for the selective synthesis of ethylene
glycol from ethylene oxide seems to be
the most promising for industrial-scale
application.

4.2. Alternative Methods of Ethylene


Glycol Production
The low selectivity of ethylene oxide production
and increasing ethylene prices warrant the search
for alternative ways of producing ethylene
glycol.
4.2.1. Direct Oxidation of Ethylene
As mentioned earlier, catalytic oxidation of
ethylene [74-85-1] with oxygen in acetic acid
has already been used on an industrial scale, but
this method was soon abandoned due to problems caused by corrosion. The yield of ethylene glycol (>90 %) was much higher than that
obtained in the more indirect route via ethylene
oxide [30].

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A more recently developed catalyst system is


based on the use of Pd(II) complexes [31]. A
mixture of PdCl2, LiCl, and NaNO3 in acetic
acid and acetic anhydride has been shown to
give a 95 % selectivity for glycol monoacetate
and glycol diacetate formation (60 100  C,
3.04 MPa) [32]. During this process, Pd(II) is
reduced to Pd(0). The precipitation of Pd(0) is
prevented because it is reoxidized to Pd(II) by
the nitrate ions. The available oxygen finally
regenerates the nitrate, thus providing a complete catalytic system.
The formation of ethylene glycol monoacetate
[542-59-6] (50 % yield) and ethylene glycol diacetate [111-55-7] (7 % yield) has also been investigated using the catalyst system PdCl
NO2 CH3CN dissolved in acetic acid. Studies
with radioactive isotopes showed that the NO2
functions as an oxidizing agent [33]. Vinyl acetate is formed as a byproduct (20 % yield). However, the catalytic action of this system is quickly
exhausted due to the precipitation of palladium
compounds.
If a PdCl2 CuCl2 CuOCOCH3 system is
used, the reaction proceeds under mild conditions (65  C, 0.5 MPa) without the formation of
a precipitate; a yield of over 90 % is obtained
[34].

Ethylene Glycol

537

In recent years, increasing attention has been


paid to Pd(II) systems as catalysts for the direct
oxidation of ethylene to ethylene glycol. In spite
of the widespread interest in this alternative,
industrial applications have yet to be realized.
4.2.2. Synthesis from C1 Units
The long-term shortage and increased price of
crude oil have led to an intensive search for
methods of producing organic intermediates
from C1 units (i.e., methods based on coal). Many
publications have appeared on the synthesis of
ethylene glycol by this approach. Only the most
important methods that rely on synthesis gas or
carbon monoxide [630-08-0] are discussed here;
they are summarized in Figure 8.
At a high pressure, carbon monoxide and
hydrogen react directly to produce ethylene glycol [35, 36]. However, the reaction is slow and
the catalyst is both sensitive and expensive [37].
Other methods involve the formation of formaldehyde [50-00-0], methanol [67-56-1] [38], or
esters of oxalic acid [144-62-7] as intermediates
[37, 39]. The only method to attain industrial
importance was that employed by Du Pont from
1940 to 1963, which used formaldehyde and

Figure 8. Production of ethylene glycol from carbon monoxide (percentages indicate approximate yields)

538

Ethylene Glycol

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glycolic acid [79-14-1] as intermediates. High


operating pressure and temperature were required, however (48 MPa, 220  C). This process
was significantly improved by the introduction of
hydrogen fluoride [7664-39-3] as a catalyst (1
2 MPa, 60  C) [40].
At the present time, none of the described
methods based on C1 units can compete with the
ethylene ! ethylene oxide ! glycol pathway.
However, if crude oil prices increase, the synthesis of ethylene glycol from C1 units will become
more economically attractive [41].

[45]. The UV absorption of fiber-grade glycol is


often used as an additional parameter for quality
control.
Gas chromatography is commonly used for
the quantitative determination of ethylene glycol. Monoethylene glycol can be detected by
oxidation with periodic acid even if di- and
triethylene glycols are also present; however,
aldehydes, glycerol, and monopropylene glycol
falsify the results [4].

7. Storage and Transportation

5. Environmental Protection and


Ecology

Pure anhydrous ethylene glycol is not aggressive


toward most metals and plastics. Since ethylene
glycol also has a low vapor pressure and is
noncaustic, it can be handled without any problems; it is transported in railroad tank cars, tank
trucks, and tank ships. Tanks are usually made of
steel; high-grade materials are only required for
special quality requirements. Nitrogen blanketing can protect ethylene glycol against oxidation.
At ambient temperatures, aluminum is resistant to pure glycol. Corrosion occurs, however,
above 100  C and hydrogen is evolved. Water,
air, and acid-producing impurities (aldehydes)
accelerate this reaction. Great care should be
taken when phenolic resins are involved, since
they are not resistant to ethylene glycol.

Ethylene glycol is readily biodegradable [42];


thus, disposal of wastewater containing this compound can proceed without major problems. The
high LC50 values of over 10 000 mg/L [43, 44]
account for its low water toxicity: LC50 crayfish
(Procambarus) 91 000 mg/L, LC50 fish (Lepomis macrochirus) 27 540 mg/L.

6. Quality Specifications and Analysis


Since ethylene glycol is produced in relatively
high purity, differences in quality are not expected. The directly synthesized product meets
high quality demands (fiber grade). The ethylene glycol produced in the wash water that is
used during ethylene oxide production is normally of a somewhat inferior quality (antifreeze
grade). The quality specifications for mono-, di-,
and triethylene glycols are compiled in Table 2

8. Derivatives
Only the most important of the many derivatives
of ethylene glycol will be discussed in this sec-

Table 2. Quality specifications of mono-, di-, and triethylene glycols [45]


Property

Purity, %
Diethylene glycol
content, wt %
Boiling range
(at 101.3 kPa),  C
Density (20  C), g/cm3
Refractive index, n20
D
Water content, wt %
Acid number, mg
of KOH/g

Method

Monoethylene glycol
Antifreeze
grade

Fiber
grade

Diethylene
glycol

Triethylene
glycol

Gas chromatography
Gas chromatography

>98.00
<0.50.

>99.80
<0.10

99.60

99.50

DIN 53171,
D 1078
DIN 51757,
D 1122
DIN 53491,
DIN 51777,
DIN 53402,

ASTM

195 200

196 199

242 247

285 295

ASTM

1.113 1.115

1.1135 1.1140

1.1160 1.1175

1.1235 1.1245

ASTM 1747
ASTM E 203
ASTM D 1613

1.431 1.433
<0.50
<0.01

1.4315 1.4320
<0.100
<0.005

1.4460 1.4475
<0.20
<0.05

1.4555 1.4565
<0.10
<0.05

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Ethylene Glycol

539

Table 3. Physical properties of mono-, di-, tri-, and tetraethylene glycols [4, 5, 46]
Property

Monoethylene glycol

Diethylene glycol

Triethylene glycol

Tetraethylene glycol

Molecular formula
CAS registry number
Mr
bp(at 101.3 kpa), o C
fp,  C
Vapor pressure (20  C), Pa
Density (20  C), g/cm3
Refractive index, n 20 d
Heat of combustion, MJ/kg
Heat of vaporization (101.3 kPa), kJ/mol
Viscosity (20  C) mPa*s
Surface tension, N/m2
Flash point,  C
Ignition temperature,  C
Lower explosive limit, vol %

HOCH2CH2OH
[107-21-1]
c62.7
197.6
13
5.3
1.1130
1.4318
19.07
52.24
19.83
4.84 (20  C)
119
410
3.2

H(OCH2CH2)2OH
[111-46-6]
106.12
244.8
8
2.7
1.1160
1.4470
22.32
52.26
36.0
4.85 (20  C)
141
390
0.7

H(OCH2CH2)3OH
[112-27-6]
150.17
287.4
7
0.5
1.1230
1.4560
23.68
61.04
49.0
4.22 (25  C)
177
370
0.9

H(OCH2CH2)4OH
[112-60-7]
194.23
decomp.
4.1
<1.3
1.1247
1.4598

tion, namely di-, tri-, and polyethylene glycols,


the methyl, ethyl, and butyl glycol ethers and the
acetate esters.

62.63
61.9
191

with the appropriate alcohol. A mixture of homologues is obtained, all displaying the following
general structure:
RO(CH2CH2O)nH

8.1. Di-, Tri-, Tetra-, and Polyethylene


Glycols
The higher homologues of ethylene glycol are
formed as byproducts during the synthesis of
ethylene oxide and monoethylene glycol or are
prepared directly by reacting monoethylene
glycol with ethylene oxide. Di-, tri-, and possibly tetraethylene glycol can be purified by distillation. For quality specifications of these
compounds, see Table 2; Table 3 shows some
of their physical properties. The temperature
dependence of the thermal conductivity, density, viscosity, and Prandtl numbers of di- and
triethylene glycol water mixtures is described
in [46].
Poly(ethylene glycols) (PEG) [25322-68-3]
are produced as mixtures of higher molecular
mass homologues (see also ! Polyoxyalkylenes) and are characterized by their mean molecular masses (e.g., PEG 400). Physical properties of some poly(ethylene glycol) mixtures are
listed in Table 4.

8.2. Ethers and Esters


Ethers. Ethylene glycol monoethers are
usually produced by reaction of ethylene oxide

The glycol monoethers can be converted to


diethers by alkylation with common alkylating
agents, such as dimethyl sulfate or alkyl halides
(Williamson synthesis). Glycol dimethyl ethers
are formed by treatment of dimethyl ether with
ethylene oxide [48]. The properties of some
ethylene glycol mono- and diethers are shown
in Tables 5 and 6, respectively; they are mainly
used as solvents.
Esters. Ethylene glycol esters are produced
from reaction of ethylene oxide and an appropriate acid and are used also as solvents. Use of a
suitable catalyst can influence the outcome of the
Table 4. Physical properties of poly(ethylene glycols) [49]
Poly(ethylene
glycol),
mean Mr

fp,  C

Refractive
index,
n70
D

Viscosity,
mPa  s*

200
600
1000
2000
10 000
20 000
35 000

ca. 50
17 22
35 40
48 52
55 60
ca. 60
ca. 60

1.458 (25  C)
1.452
1.453
1.454
1.456
1.456
1.456

60 70 (100 %)
16 19
24 29
50 60
530 1000
2700 3500
11 000 14 000

Values refer to a 50 wt % aqueous poly(ethylene glycol) solution


except where otherwise stated.

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Ethylene Glycol

Vol. 13

Table 5. Physical properties of some ethylene glycol monoalkyl ethers, RO(CH2CH2O)nH [4, 5]
R

n CAS
registry
number

Mr

fp,  C

bp
Density Refractive Specific heat Vapor
Flash point, Ignition
Explosive


(101.3 kPa), (20  C), index, n20
pressure
C
temperature, limits,
D (20 C),


C
kg/m3
J g1 K1
(20  C), Pa
C
vol %

CH3
C2H5
C4H9
CH3
C2H5
C4H9
CH3
C2H5

1
1
1
2
2
2
3
3

76.094
90.120
118.172
120.146
134.172
162.224
164.198
178.224

 85.1
100.0
 70.4
 50.0
 54.0
 68.1
 38.2
 18.7

124.50
135.10
171.20
194.10
201.90
230.60
249.00
255.50

[109-86-4]
[110-80-5]
[111-76-2]
[111-77-3]
[111-90-0]
[112-34-5]
[112-35-6]
[112-50-5]

964.6
929.7
900.8
1021.0
989.0
953.0
1047.5
1020.0

1.4024
1.4079
1.4194
1.4265
1.4275
1.4316
1.4381
1.4380

reaction so as to produce monoesters (sodium


acetate) or diesters (sulfuric acid). Glycol monoethers can be converted to the corresponding
ether esters by the usual methods. Some important properties of ethylene glycol esters and ether
esters are listed in Table 7.
Trade Names. Some common trade names
of ethylene glycol ethers and esters are as
follows:
Monoethylene Glycol Derivatives. Monomethyl ether: Methyl Cellosolve Solvent,
Dowanol EM Glycol Ether, Methyl Oxitol
Glycol. Monoethyl ether: Cellosolve Solvent,
Dowanol EE Glycol Ether. Monobutyl ether:
Butyl Cellosolve Solvent, Dowanol EB Glycol
Ether, Butyl Oxitol Glycol. Dimethyl ether (also
known as glyme): Dimethyl Cellosolve Solvent.
Diethyl ether: Diethyl Cellosolve Solvent.
Monomethyl ether acetate: Methyl Cellosolve
Acetate. Monoethyl ether acetate: Cellosolve
Acetate, Poly-solv EE Acetate.
Diethylene Glycol Derivatives. Monomethyl
ether: Methyl Carbitol Solvent, Dowanol DM
Glycol Ether. Monoethyl ether: Carbitol Solvent,
Dowanol DE Glycol Ether. Monomethyl ether

2.24
930
2.32
530
2.44
80
2.15
24
2.31
17
2.29
4
2.18
2.17 (15  C)
0.4

38
40
66
90
93
99
118
195

285
215
225
215
190
195

2.4
1.8
1.1
1.6
1.8
0.7

20.6
15.7
10.6
16.1
12.2
5.9

acetate: Methyl Carbitol Acetate. Monoethyl


ether acetate: Carbitol Acetate. Monobutyl ether
acetate: Butyl Carbitol Acetate.
Diethylene glycol dimethyl ether is also
known as diglyme.
Triethylene Glycol Derivatives. Monomethyl ether: Dowanol TM Glycol Ether.

9. Uses
Ethylene glycol lowers the freezing point of
water (see Fig. 1). Its ease of handling makes it
a perfect antifreeze [51], which accounts for over
50 % of its commercial uses (! Antifreezes).
Commercial antifreezes based on glycol also
contain corrosion inhibitors and are used, for
example, in motor vehicles, solar energy units,
heat pumps, water heating systems, and industrial cooling systems. Protection against freezing is
directly related to the glycol concentration; 60 %
glycol prevents freezing down to a temperature
of 55  C. There is little point using higher
concentrations because the freezing point then
starts to increase (Fig. 1).

Table 6. Physical properties of some ethylene glycol dialkyl ethers RO(CH2CH2O)n-R [2, 4, 50]
R

n CAS
registry
number

Mr

fp,  C bp
Density Refractive Specific heat Vapor
Flash point, Ignition
Lower

(20  C),
pressure
C
temperature, explosive
(101.3 kPa), (20  C), index, n20
D


C
kg/m3
J g1 K1
(20  C), Pa
C
limit,
vol %

CH3
C2H5
C4H9
CH3
C2H5
C4H9
CH3

1
1
1
2
2
2
3

90.120
118.172
174.276
134.172
162.224
218.328
178.224

58.0
74.0
69.1
64.0
44.3
60.2
45.0

[110-71-4]
[629-14-1]
[112-48-1]
[111-96-6]
[112-36-7]
[112-73-2]
[112-35-6]

85.2
121.4
203.6
163.0
188.4
254.6
216.0

867.0
841.0
836.0
944.0
906.6
883.8
987.0

1.3796
1.3920
1.4131
1.4078
1.4115
1.4233
1.4233

2.01
2.04
2.10
1.80

8100.0
1250.0
27.0
267.0
(15  C)
51.0
(13  C)
1.3
120.0

6
35
85
51
82
118
113

200
205

1.6

1.4

195

0.7

Vol. 13

Ethylene Glycol

541

Table 7. Physical properties of some ethylene glycol acetates and ether acetates [4]
Compound

CAS registry Mr
number

fp,  C bp
Density Refractive Ignition Flash Explosive
(101.3 kPa), (20  C), index, n20
tempera- point, limits,
D

C
kg/m3
ture,  C  C
vol %

Ethylene glycol monoacetate


Ethylene glycol diacetate
Ethylene glycol methyl ether acetate
Ethylene glycol ethyl ether acetate
Ethylene glycol butyl ether acetate
Diethylene glycol methyl ether acetate
Diethylene glycol ethyl ether acetate
Diethylene glycol butyl ether acetate

[542-59-6]
[111-55-7]
[110-49-6]
[111-15-9]
[112-07-2]
[629-38-9]
[112-15-2]
[124-17-4]

80.0
31.0
65.1
61.7
63.5
99.3
25.0
32.2

104.10
146.10
118.13
132.16
160.21
162.19
176.21
204.26

Ethylene glycol is also a commercially important raw material for the manufacture of
polyester fibers, chiefly poly(ethylene terephthalate) (! Fibers, 4. Synthetic Organic).
This application consumes ca. 40 % of the total
ethylene glycol production. Polyesters are,
however, used for other purposes, e.g., for
producing recyclable bottles (! Polyesters).
Other minor uses of ethylene glycol are as a
humectant (moisture-retaining agent), plasticizer, softener, hydraulic fluid, and solvent
[52].
Ethylene Glycol Derivatives, mainly the
ethers and esters, are frequently employed as
reaction media, as absorption fluids, and as
solvents for dyes, lacquers, and various cellulose
products (cellulose esters, ethers, and nitrocellulose) [53].
Diethylene Glycol serves as a solvent, softener (cork, adhesives, paper, etc.), dye additive
(printing and stamping inks), deicing agent for
runways and aircraft [54], and a drying agent for
gases (e.g., natural gas) [55].
Triethylene Glycol is used for the same
purposes as diethylene glycol (e.g., as a solvent,
plasticizer, and drying agent for gases) [56].
Poly(ethylene Glycols) with varying molecular masses find numerous uses in the pharmaceutical industry (e.g., in ointments, liquids,
and tabletting) and the cosmetic industry (e.g.,
creams, lotions, pastes, cosmetic sticks, and
soaps). They are also used in the textile industry
(e.g., cleaning and dyeing aids), in the rubber
industry (e.g., lubricants and mold parting

182.0
190.5
145.0
156.4
192.3
209.1
217.4
246.7

1110
1106
1006
974
942
1041
1011
981

1.4209
1.4159
1.4019
1.4058
1.4138
1.4209
1.4213
1.4262

410
390
355

290

102
105
49
54
74
110
112
116

7.8 27.7
1.7 8.2
3.18 10.1
1.66 8.37

agents), and in ceramics (e.g., bonding agents


and plasticizers) [57].

10. Economic Aspects


Ethylene glycol is one of the major products of
the chemical industry. Its economic importance
is founded on its two major commercial uses as
an antifreeze and for fiber production. Since
ethylene glycol is currently produced exclusively
from ethylene oxide (! Ethylene Oxide), production plants are always located close to plants
that produce ethylene oxide. The proportion
of ethylene oxide that is converted to glycol
depends on the local conditions, such as transport
facilities and the market situation. Almost all of
the ethylene oxide produced in recently installed
plants in Saudi Arabia is, for example, converted
to ethylene glycol because the domestic market
for ethylene oxide is negligible and because
ethylene glycol is easier to transport than ethylene oxide.
Detailed information about the glycol capacities of individual plants is difficult to obtain, but
an estimated 60 % of the total world production
of ethylene oxide is converted to ethylene
glycol. Therefore, the worldwide ethylene oxide
production capacity of 8  106 t corresponds to
an annual ethylene glycol production of
6.7  106 t.
About 50 % of the ethylene glycol that is
produced is used in antifreeze. Another 40 % is
channeled into the fiber industry. Consequently,
the ethylene glycol demand is closely connected
to the development of these two sectors. Surplus
capacities and growing competition for market
shares are expected on account of increasing

542

Ethylene Glycol

glycol capacities not only in Saudi Arabia, but


also in the Eastern Bloc. Japan has already
reduced its glycol capacities considerably [58].
In view of the increasing price of crude oil,
alternative production methods based on synthesis gas hitherto still in the experimental phase
are likely to become more important and increasingly competitive.

11. Toxicology and Occupational


Health
11.1. Ethylene Glycol
Oral Toxicity. The oral LD50 values of
ethylene glycol are 14 15 g/kg [59, 60] for
mice and ca. 8 g/kg [61] for rats. Oral toxicity in
humans is higher, 1.4 g/kg can be lethal [59].
In rats, long-term administration of ethylene
glycol in food at concentrations of 10.0 and
20.0 g/kg led to formation of bladder stones
(calcium oxalate), damage to the renal tubules,
and centrolobular fatty degeneration of the liver
[62]. In other investigations, comparable changes
were already apparent at a concentration of 5.0 g/
kg, no changes were observed at 2.0 g/kg [63].
No changes were observed in the kidneys of
monkeys fed a diet providing a maximal daily
dose of 0.17 g/kg of body mass over a period of
three years [64]. However, addition of ethylene
glycol to the drinking water given to monkeys at a
concentration corresponding to a daily dose of
0.24 g/kg of body mass led to the formation of
oxalate crystals in the kidneys after about five
months. Oxalate crystals were also formed in the
brains of monkeys given very high doses
(10 wt %) in drinking water [65].
Eye and Skin Irritation. Introduction of a
single dose of ethylene glycol into the conjunctival sac does not affect the rabbit eye [66], but
repeated administration leads to mild conjunctivitis [67]. Ethylene glycol vapor at a concentration of 17 mg/m3 produces ocular damage in
humans [68]. No effects were observed in the
eyes of monkeys exposed to a vapor concentration of 265 mg/m3 [68].
Ethylene glycol has not been shown to irritate
mucous membranes. Repeated exposure of the
skin to ethylene glycol can cause mild irritation,
similar to that produced by glycerol.

Vol. 13

Inhalation. The inhalative toxicity of an


atmosphere saturated with ethylene glycol
(0.5 mg/L) is low. Rats tolerated this concentration for four weeks without any permanent
injuries, only mild narcosis was observed [69].
No adverse effects were detected in rats,
rabbits, guinea pigs, dogs, and monkeys exposed
to an ethylene glycol concentration of 57 mg/L
for six weeks [70]. Monkeys survived after
inhaling concentrations of 600 mg/m3 administered as an aerosol over a period of several
months.
Human volunteers exposed to maximal concentrations of 67 mg/m3 for one month reported
some irritation of the nasal mucous membranes
and occasionally headache. The presence of ethylene glycol in the inhaled atmosphere was perceived at concentrations above 140 mg/m3 [71].
A concentration of 200 mg/m3 was found to be
intolerable [72]. Rats, rabbits, dogs, and monkeys that inhaled pure oxygen containing
100 mL/m3 of ethylene glycol at a pressure of
34.5 kPa for three weeks did not show any
adverse effects apart from local irritation [73].
Mutagenicity and Carcinogenicity. Ethylene glycol gives a negative result in the Ames
test [74, 75]. Many studies have been
performed on its carcinogenicity [64, 76, 77].
Rats were fed with diets containing ethylene
glycol concentrations corresponding to 1000,
200, and 40 mg/kg of body mass; no carcinogenic effects were observed. However, typical
formation of oxalate crystals in the kidneys and
other organs was found [78]. Similar experiments did not increase the incidence of tumor
formation in mice [79].
Reproduction. In a study extending over
three generations, ethylene glycol was added to
the diet fed to rats at a concentration of 0.04, 0.2,
and 1.0 g kg1 d1. The fertility and viability of
the offspring were not affected by this treatment
[80].
Teratogenic effects were not detected in rats
receiving maximal feed concentrations of
1000 mg/kg, only a mild fetal toxicity was observed [81]. Teratogenic and fetotoxic effects
were produced in mice and rats after administration of very high doses (1.25, 2.50, and 5.00 g/kg
of body mass) in the form of a bolus with the aid
of an esophageal probe [82].

Vol. 13

Ethylene Glycol

Metabolism. In the body, ethylene glycol is


degraded by alcohol dehydrogenase to form glycolaldehyde, which is further degraded by an
aldehyde oxidase to produce glyoxal. Glyoxal is
subsequently metabolized to glycolic and
glyoxylic acids, from which oxalic acid, formic
acid, glycine, 2-oxo-4-hydroxygluconate, 2-hydroxy-3-oxoadipate and oxomalate are formed
[83, p. 3827].

543

stones is attributed to contamination of the


diethylene glycol with monoethylene glycol
(see Section 11.1) [87, 88]. The low cumulative
toxicity of diethylene glycol has been confirmed
[8991].
Diethylene glycol does not irritate the eyes or
skin [92]; absorption by the skin is extremely low
[93]. Diethylene glycol does not affect the fertility of rats [94]. It does not display mutagenicity in
the Ames test [95]; other studies also suggest that
the compound is not carcinogenic [87, 88].

11.2. Ethylene Glycol Derivatives


Toxicity data and exposure limits for ethylene
glycols and some monoethylene glycol derivatives are listed in Table 8.
Diethylene Glycol has a low acute oral toxicity (see Table 8). A LDLo value of 1.0 mL/kg
is often erroneously cited but this value was
determined using a preparation that contained
sulfanilimide [85].
In long-term studies performed over a period
of two years, dietary levels of 1, 2, and 4 %
diethylene glycol administered to rats produced
calcium oxalate stones with associated kidney
and liver damage [86]. Chronic mechanical
irritation of the bladder epithelium by the resulting bladder stones led to the formation of
benign tumors. Production of calcium oxalate

Triethylene Glycol has an extremely low


oral toxicity when given either in a single dose
(see Table 8) or in repeated doses [86, 96]. This
compound causes only slight irritation of the skin
and mucous membranes, it is not teratogenic
[97].
Tetraethylene Glycol is, like triethylene
glycol, nontoxic (see Table 8).
Poly(Ethylene Glycols) have an extremely
low acute oral toxicity (LD50 in rats > 30 g/kg)
which decreases as their molecular mass increases [98]. Studies on rats [98] and dogs [99]
have shown that their cumulative toxicity is also
very low.
Irritation of the skin and mucous membranes
in humans and animals is slight. When applied to

Table 8. Toxicity data and exposure limits for ethylene glycols and ethylene glycol derivatives
Compound

Ethylene glycols
Monoethylene glycol
Diethylene glycol
Triethylene glycol
Tetraethylene glycol
Monoethylene glycol derivatives
Monomethyl ether
(methoxyethanol)
Monomethyl ether acetate
(methoxyethyl acetate)
Monoethyl ether
(ethoxyethanol)
Monoethyl ether acetate
(ethoxyethyl acetate)
Monobutyl ether
(butoxyethanol)
Monobutyl ether acetate
(butoxyethyl acetate)
*

mL/kg

Single oral
LD50 in rats,
g/kg

Reference

MAK,
ppm

TLV-TWA,
ppm

8
20.8
22.1
30.8*

[61]
[61]
[61]
[83, p. 3843]

10
10

50

3.4

[84]

3.93

[61]

5.5

[84]

5.1

[61]

2.5

[84]

20

25

20

544

Ethylene Glycol

the skin, pure poly(ethylene glycols) do not cause


sensitization [98, 100, 101] and are nontoxic
[98]. Poly(ethylene glycols) with a molecular
mass < 1000 are absorbed in the intestine and
excreted in the urine and feces. Intestinal absorption decreases markedly as the molecular mass
increases [102104].

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Ethylene Glycol

84

85
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90

91
92
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Further Reading
G. P. Chiusoli, P. M. Maitlis (eds.): Metal-catalysis in Industrial Organic Processes, Royal Society of Chemistry,
Cambridge, UK 2006.
R. J. Farn (ed.): Chemistry and Technology of Surfactants,
Blackwell, Oxford, UK 2006.
M. W. Forkner, J. H. Robson, W. M. Snellings, A. E. Martin,
F. H. Murphy, T. E. Parsons: Glycols, Kirk Othmer

546

Ethylene Glycol

Encyclopedia of Chemical Technology, John Wiley &


Sons, Hoboken, NJ, online DOI: 10.1002/
0471238961.0520082506151811.a01.pub2.
J. Hagen: Industrial Catalysis, 2nd ed., Wiley-VCH,
Weinheim 2006.
M. Kjellin, I. Johansson (eds.): Surfactants from Renewable
Resources, Wiley, Chichester 2010.

Vol. 13
H. K. Phlegm: The Role of the Chemist in Automotive Design,
CRC Taylor & Francis, Boca Raton, FL 2009.
J. Tulla-Puche, F. Albericio: The Power of Functional
Resins in Organic Synthesis, Wiley-VCH, Weinheim
2008.
U. Zoller, P. Sosis: Handbook of Detergents, CRC Press,
Boca Raton, FL 2009.

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