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. Introduction. . . . . . . . . . . . . . . . . . . . . . . . 531 7. Storage and Transportation. . . . . . . . . . . . 538

2. Physical Properties . . . . . . . . . . . . . . . . . . 531 8. Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . 538
3. Chemical Properties . . . . . . . . . . . . . . . . . 532 8.1. Di-, Tri-, Tetra-, and Polyethylene Glycols 539
4. Production . . . . . . . . . . . . . . . . . . . . . . . . . 534 8.2. Ethers and Esters. . . . . . . . . . . . . . . . . . . . 539
4.1. Ethylene Oxide Hydrolysis. . . . . . . . . . . . . 534 9. Uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
4.1.1. Current Production Method . . . . . . . . . . . . . 534 10. Economic Aspects . . . . . . . . . . . . . . . . . . . 541
4.1.2. Possible Developments . . . . . . . . . . . . . . . . 535 11. Toxicology and Occupational Health . . . . . 542
4.2. Alternative Methods of Ethylene Glycol 11.1. Ethylene Glycol . . . . . . . . . . . . . . . . . . . . . 542
Production . . . . . . . . . . . . . . . . . . . . . . . . . 536 11.2. Ethylene Glycol Derivatives. . . . . . . . . . . . 543
4.2.1. Direct Oxidation of Ethylene . . . . . . . . . . . . 536 References . . . . . . . . . . . . . . . . . . . . . . . . . 544
4.2.2. Synthesis from C1 Units. . . . . . . . . . . . . . . . 537
5. Environmental Protection and Ecology . . . 538
6. Quality Specifications and Analysis . . . . . . 538

1. Introduction 2. Physical Properties

Ethylene glycol [107-21-1,] 1,2-ethanediol, Ethylene glycol is a clear, colorless, odorless
HOCH2CH2OH, Mr62.07, usually called glycol, liquid with a sweet taste. It is hygroscopic and
is the simplest diol. It was first prepared by completely miscible with many polar solvents,
WURTZ in 1859 [1]; treatment of 1,2-dibro- such as water, alcohols, glycol ethers, and
moethane [106-93-4] with silver acetate yielded acetone. Its solubility is low, however, in non-
ethylene glycol diacetate, which was then hydro- polar solvents, such as benzene, toluene, dichlo-
lyzed to ethylene glycol. roethane, and chloroform. The UV, IR, NMR,
Ethylene glycol was first used industrially in and Raman spectra of ethylene glycol are given
place of glycerol during World War I as an in [3]. Following are some of the physical prop-
intermediate for explosives (ethylene glycol erties of ethylene glycol [46]:
dinitrate) [2], but has since developed into a
major industrial product.
The worldwide capacity for the production of
bp at 101.3 kPa 197.60
C
ethylene glycol via the hydrolysis of ethylene fp 13.00
C
oxide [75-21-8] (! Ethylene Oxide) is estimat- Density at 20
C 1.1135 g/cm3
ed to be ca. 7x106 t/a. Refractive index, n20
D 1.4318
Heat of vaporization at 101.3 kPa 52.24 kJ/mol
Ethylene glycol is used mainly as an anti-
Heat of combustion 19.07 MJ/kg
freeze in automobile radiators (! Antifreezes) Critical data
and as a raw material for the manufacture of Temperature 372
C
polyester fibers (! Fibers, 4. Synthetic Organic; Pressure 6515.73 kPa
! Polyesters). Volume 0.186 L/mol

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

DOI: 10.1002/14356007.a10_101
532 Ethylene Glycol Vol. 13


Flash point 111 C
Ignition temperature 410
C
Lower explosive limit 3.20 vol %
Upper explosive limit 53 vol %
Viscosity at 20
C 19.83 mPa  s
Cubic expansion coefficient at 20
C 0.62103 K1

Ethylene glycol is difficult to crystallize;

when cooled, it forms a highly viscous, super-
cooled 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 temper-
ature dependencies of the thermal conductivity, Figure 2. Temperature dependence of the thermal conduc-
density, and viscosity of ethylene glycol and tivity of ethylene glycol water mixtures
ethylene glycol water mixtures are shown in Ethylene glycol content, mol %: a) 0; b) 25; c) 55;
Figures 23, and 4 respectively [7]. The Prandtl d) 75; e) 100
numbers (the ratio of the viscosity to the thermal
conductivity) derived from these values are characteristics and industrially important reac-
given in Figure 5 [7]. The vapor pressures of tions of ethylene glycol are considered here. The
ethylene glycol water mixtures have been two adjacent hydroxyl groups allow cyclization,
obtained from [8] by interpolation and are listed and polycondensation; one or both of these
in Table 1. functional groups may, of course, also react to
give other derivatives.

3. Chemical Properties Oxidation. Ethylene glycol is easily

oxidized to form a number of aldehydes and
Ethylene glycol, like other alcohols, undergoes carboxylic acids by oxygen, nitric acid, and other
the reactions typical of its hydroxyl groups,
which are described elsewhere ( ! Alcohols,
Aliphatic). Thus, only the special chemical

Figure 3. Temperature dependence of the density of ethylene

Figure 1. Freezing points of mono- and diethylene glycol glycol water mixtures
water mixtures Ethylene glycol content, mol %: a) 0; b) 26.1; c) 50.95;
a) Monoethylene glycol; b) Diethylene glycol d) 76.9; e) 100
Vol. 13 Ethylene Glycol 533

Table 1. Vapor pressure of ethylene glycol water mixtures

Water content, Vapor pressure, in kPa at

wt %
65.1
C 77.7
C 90.3
C

0 0.30 0.52 1.20

10 6.61 11.65 19.73
20 11.30 19.68 33.01
30 14.70 25.45 42.49
40 17.10 29.68 49.37
50 18.81 32.92 54.60
60 20.16 35.58 58.87
70 21.45 37.92 62.60
80 22.98 40.05 65.98
90 25.08 41.91 68.93
100 28.04 43.34 71.10

oxidizing agents. The typical products derived

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
from the alcoholic functions are glycolaldehyde
(HOCH2CHO) [141-46-8,] glycolic acid
(HOCH2COOH) [79-14-1,] glyoxal (CHO-
CHO) [107-22-2,] glyoxylic acid (HCOCOOH)
[298-12-4,] oxalic acid (HOOCCOOH) [144-
62-7,] 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, period-
ate, 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]:

Acetalization to the cyclic 1,3-dioxolane

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
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.
534 Ethylene Glycol
1,3-Dioxolanes can also be formed from
ethylene glycol by transacetalization. Examples
are the reactions of ethylene glycol with ortho-
formates [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 gly-
col can be alkylated or acylated by the custom-
ary methods to form ethers or esters, respective-
ly. However, the presence of two hydroxyl
groups leads to the formation of both mono-
and 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).
Ethoxylation. Ethylene glycol reacts with
ethylene oxide to form di-, tri-, tetra-, and poly-
ethylene glycols. The proportions of these gly-
cols found in the reaction product are determined
by the catalyst system that is used and the glycol
excess. A considerable excess of glycol is re-
quired to obtain the lower homologues in a
satisfactory yield. This reaction is rarely used
Vol. 13
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 tempe-
rature in the presence of a base such as sodium
hydroxide. Fragmentation of the molecule be-
gins 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 industri-
ally until World War I. Its synthesis was then
based on the hydrolysis of ethylene oxide [75-
21-8] 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 con-
sulted 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
Only one method is currently used for the indus-
trial 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
Vol. 13
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 composi-
tion 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
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)
Ethylene Glycol 535
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 homo-
logues:
After leaving the reactor, the product mix-
ture 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 pro-
ducts, 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].
4.1.2. Possible Developments
The glycol production method described in
Section 4.1.1 is the only one of current industrial
536 Ethylene Glycol Vol. 13

importance. It is simple, but has some major double the molar quantity of water is required for
drawbacks: this reaction.

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 triethy-
lene glycol. According to a Halcon patent, ethylene ox-
3. Energy consumption for the distillation of the ide can be extracted from the aqueous solution,
large amount of excess water is high. formed during its production, with supercriti-
cal carbon dioxide [29]. An ethylene oxide
Therefore, much research has been carried out to carbon dioxide solution is obtained, which
improve this process. The search for better silver reacts to form ethylene carbonate. Hydrolysis
catalysts is an objective for point 1 (! Ethylene of the ethylene carbonate then yields ethylene
Oxide). Points 2 and 3 must be considered to- glycol. Possible catalysts for this reaction are
gether, since higher selectivity for ethylene oxide quaternary ammonium and phosphonium salts,
hydrolysis automatically reduces the excess of such as R4NHal, R4PHal, or Ph3PCH3I. Pro-
water required. blems such as product separation and catalyst
Many catalysts have been described in the feedback still need to be resolved, but this
literature that are able to optimize selectivity method for the selective synthesis of ethylene
or lower the reaction temperature and the glycol from ethylene oxide seems to be
required excess of water. Acids and bases are the most promising for industrial-scale
known to accelerate the reaction rate. The application.
kinetics of the acid [19] and base [20] catalysis
of ethylene oxide hydrolysis have been thor-
oughly investigated; mechanisms are discussed 4.2. Alternative Methods of Ethylene
in [21]. The industrial feasability of catalysis Glycol Production
with ion-exchange columns in the liquid phase
[22, 23] and the gas phase [24] has been tested. The low selectivity of ethylene oxide production
Although the use of catalysts allowed the and increasing ethylene prices warrant the search
reaction temperature to be lowered, selectivity for alternative ways of producing ethylene
was not significantly enhanced. Furthermore, glycol.
the catalyst needed to be separated and either
fed back into the reaction mixture or replaced.
4.2.1. Direct Oxidation of Ethylene
As a result of these disadvantages, these types
of catalysis have not proved to be of commer-
As mentioned earlier, catalytic oxidation of
cial use. However, catalysts that improve
ethylene [74-85-1] with oxygen in acetic acid
selectivity have been described in patents; they
has already been used on an industrial scale, but
include molybdates [25], vanadates [26], ion
this method was soon abandoned due to pro-
exchangers [27], and organic antimony com-
blems caused by corrosion. The yield of ethyl-
pounds [28]. However, their advantages do not
ene glycol (>90 %) was much higher than that
yet seem to justify their use on an industrial
obtained in the more indirect route via ethylene
scale.
oxide [30].
The selective synthesis of ethylene glycol via
the intermediate ethylene carbonate (1,3-dioxo-
lan-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
Vol. 13
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 com-
plete catalytic system.
The formation of ethylene glycol monoacetate
[542-59-6] (50 % yield) and ethylene glycol dia-
cetate [111-55-7] (7 % yield) has also been in-
vestigated 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 ace-
tate is formed as a byproduct (20 % yield). How-
ever, 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 condi-
tions (65
C, 0.5 MPa) without the formation of
a precipitate; a yield of over 90 % is obtained
[34].
Figure 8. Production of ethylene glycol from carbon monoxide (percentages indicate approximate yields)
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 gly-
col [35, 36]. However, the reaction is slow and
the catalyst is both sensitive and expensive [37].
Other methods involve the formation of formal-
dehyde [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
538 Ethylene Glycol Vol. 13

glycolic acid [79-14-1] as intermediates. High
operating pressure and temperature were re-
quired, 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 synthe-
sis of ethylene glycol from C1 units will become
more economically attractive [41].
5. Environmental Protection and
Ecology
Ethylene glycol is readily biodegradable [42];
thus, disposal of wastewater containing this com-
pound 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 (Lepo-
mis macrochirus) 27 540 mg/L.
6. Quality Specifications and Analysis
Since ethylene glycol is produced in relatively
high purity, differences in quality are not ex-
pected. The directly synthesized product meets
high quality demands (fiber grade). The eth-
ylene glycol produced in the wash water that is
used during ethylene oxide production is normal-
ly of a somewhat inferior quality (antifreeze
grade). The quality specifications for mono-, di-,
and triethylene glycols are compiled in Table 2
[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 gly-
col. 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
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 prob-
lems; 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 blanket-
ing can protect ethylene glycol against oxidation.
At ambient temperatures, aluminum is resis-
tant 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.
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 Method Monoethylene glycol

Antifreeze Fiber Diethylene Triethylene

grade grade glycol glycol

Purity, % Gas chromatography >98.00 >99.80 99.60 99.50

Diethylene glycol Gas chromatography <0.50. <0.10
content, wt %
Boiling range DIN 53171, ASTM 195 200 196 199 242 247 285 295
(at 101.3 kPa),
C D 1078
Density (20
C), g/cm3 DIN 51757, ASTM 1.113 1.115 1.1135 1.1140 1.1160 1.1175 1.1235 1.1245
D 1122
Refractive index, n20
D DIN 53491, ASTM 1747 1.431 1.433 1.4315 1.4320 1.4460 1.4475 1.4555 1.4565
Water content, wt % DIN 51777, ASTM E 203 <0.50 <0.100 <0.20 <0.10
Acid number, mg DIN 53402, ASTM D 1613 <0.01 <0.005 <0.05 <0.05
of KOH/g
Vol. 13 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 HOCH2CH2OH H(OCH2CH2)2OH H(OCH2CH2)3OH H(OCH2CH2)4OH

CAS registry number [107-21-1] [111-46-6] [112-27-6] [112-60-7]
Mr c62.7 106.12 150.17 194.23
bp(at 101.3 kpa), o C 197.6 244.8 287.4 decomp.
fp,
C 13 8 7 4.1
Vapor pressure (20
C), Pa 5.3 2.7 0.5 <1.3
Density (20
C), g/cm3 1.1130 1.1160 1.1230 1.1247
Refractive index, n 20 d 1.4318 1.4470 1.4560 1.4598
Heat of combustion, MJ/kg 19.07 22.32 23.68
Heat of vaporization (101.3 kPa), kJ/mol 52.24 52.26 61.04 62.63
Viscosity (20
C) mPa*s 19.83 36.0 49.0 61.9
Surface tension, N/m2 4.84 (20
C) 4.85 (20
C) 4.22 (25
C)
Flash point,
C 119 141 177 191
Ignition temperature,
C 410 390 370
Lower explosive limit, vol % 3.2 0.7 0.9

tion, namely di-, tri-, and polyethylene glycols, with the appropriate alcohol. A mixture of homo-
the methyl, ethyl, and butyl glycol ethers and the logues is obtained, all displaying the following
acetate esters. general structure:

RO(CH2CH2O)nH
8.1. Di-, Tri-, Tetra-, and Polyethylene
Glycols The glycol monoethers can be converted to
diethers by alkylation with common alkylating
The higher homologues of ethylene glycol are agents, such as dimethyl sulfate or alkyl halides
formed as byproducts during the synthesis of (Williamson synthesis). Glycol dimethyl ethers
ethylene oxide and monoethylene glycol or are are formed by treatment of dimethyl ether with
prepared directly by reacting monoethylene ethylene oxide [48]. The properties of some
glycol with ethylene oxide. Di-, tri-, and possi- ethylene glycol mono- and diethers are shown
bly tetraethylene glycol can be purified by dis- in Tables 5 and 6, respectively; they are mainly
tillation. For quality specifications of these used as solvents.
compounds, see Table 2; Table 3 shows some
of their physical properties. The temperature Esters. Ethylene glycol esters are produced
dependence of the thermal conductivity, den- from reaction of ethylene oxide and an appropri-
sity, viscosity, and Prandtl numbers of di- and ate acid and are used also as solvents. Use of a
triethylene glycol water mixtures is described suitable catalyst can influence the outcome of the
in [46].
Poly(ethylene glycols) (PEG) [25322-68-3]
are produced as mixtures of higher molecular Table 4. Physical properties of poly(ethylene glycols) [49]
mass homologues (see also ! Polyoxyalky- Poly(ethylene fp,
C Refractive Viscosity,
lenes) and are characterized by their mean mo- glycol), index, mPa  s*
lecular masses (e.g., PEG 400). Physical proper- mean Mr n70
D
ties of some poly(ethylene glycol) mixtures are 200 ca. 50 1.458 (25
C) 60 70 (100 %)
listed in Table 4. 600 17 22 1.452 16 19
1000 35 40 1.453 24 29
2000 48 52 1.454 50 60
10 000 55 60 1.456 530 1000
8.2. Ethers and Esters 20 000 ca. 60 1.456 2700 3500
35 000 ca. 60 1.456 11 000 14 000
Ethers. Ethylene glycol monoethers are *
Values refer to a 50 wt % aqueous poly(ethylene glycol) solution
usually produced by reaction of ethylene oxide except where otherwise stated.
540 Ethylene Glycol Vol. 13

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

R n CAS Mr fp,
C bp Density Refractive Specific heat Vapor Flash point, Ignition Explosive
registry (101.3 kPa), (20
C), index, n20

D (20 C), pressure

C temperature, limits,
number

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

C vol %

CH3 1 [109-86-4] 76.094  85.1 124.50 964.6 1.4024 2.24 930 38 285 2.4 20.6
C2H5 1 [110-80-5] 90.120 100.0 135.10 929.7 1.4079 2.32 530 40 215 1.8 15.7
C4H9 1 [111-76-2] 118.172  70.4 171.20 900.8 1.4194 2.44 80 66 225 1.1 10.6
CH3 2 [111-77-3] 120.146  50.0 194.10 1021.0 1.4265 2.15 24 90 215 1.6 16.1
C2H5 2 [111-90-0] 134.172  54.0 201.90 989.0 1.4275 2.31 17 93 190 1.8 12.2
C4H9 2 [112-34-5] 162.224  68.1 230.60 953.0 1.4316 2.29 4 99 195 0.7 5.9
CH3 3 [112-35-6] 164.198  38.2 249.00 1047.5 1.4381 2.18 118
C2H5 3 [112-50-5] 178.224  18.7 255.50 1020.0 1.4380 2.17 (15
C) 0.4 195

reaction so as to produce monoesters (sodium acetate: Methyl Carbitol Acetate. Monoethyl

acetate) or diesters (sulfuric acid). Glycol mono-
ethers can be converted to the corresponding
ether esters by the usual methods. Some impor-
tant 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. Mono-
methyl 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
ether acetate: Carbitol Acetate. Monobutyl ether
acetate: Butyl Carbitol Acetate.
Diethylene glycol dimethyl ether is also
known as diglyme.
Triethylene Glycol Derivatives. Mono-
methyl 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 industri-
al 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 Mr fp,
C bp Density Refractive Specific heat Vapor Flash point, Ignition Lower
registry (101.3 kPa), (20
C), index, n20
D (20
C), pressure

C temperature, explosive
number

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

C limit,
vol %

CH3 1 [110-71-4] 90.120 58.0 85.2 867.0 1.3796 8100.0 6 200 1.6
C2H5 1 [629-14-1] 118.172 74.0 121.4 841.0 1.3920 1250.0 35 205
C4H9 1 [112-48-1] 174.276 69.1 203.6 836.0 1.4131 2.01 27.0 85
CH3 2 [111-96-6] 134.172 64.0 163.0 944.0 1.4078 2.04 267.0 51 1.4
C2H5 2 [112-36-7] 162.224 44.3 188.4 906.6 1.4115 2.10 (15
C) 51.0 82
C4H9 2 [112-73-2] 218.328 60.2 254.6 883.8 1.4233 1.80 (13
C) 1.3 118
CH3 3 [112-35-6] 178.224 45.0 216.0 987.0 1.4233 120.0 113 195 0.7
Vol. 13 Ethylene Glycol 541

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

Compound CAS registry Mr fp,
C bp Density Refractive Ignition Flash Explosive

number (101.3 kPa), (20
C), index, n20
D tempera- point, limits,


C kg/m3 ture,
C
C vol %

Ethylene glycol monoacetate [542-59-6] 104.10 80.0 182.0 1110 1.4209 102 7.8 27.7
Ethylene glycol diacetate [111-55-7] 146.10 31.0 190.5 1106 1.4159 105
Ethylene glycol methyl ether acetate [110-49-6] 118.13 65.1 145.0 1006 1.4019 410 49 1.7 8.2
Ethylene glycol ethyl ether acetate [111-15-9] 132.16 61.7 156.4 974 1.4058 390 54 3.18 10.1
Ethylene glycol butyl ether acetate [112-07-2] 160.21 63.5 192.3 942 1.4138 355 74 1.66 8.37
Diethylene glycol methyl ether acetate [629-38-9] 162.19 99.3 209.1 1041 1.4209 110
Diethylene glycol ethyl ether acetate [112-15-2] 176.21 25.0 217.4 1011 1.4213 112
Diethylene glycol butyl ether acetate [124-17-4] 204.26 32.2 246.7 981 1.4262 290 116

Ethylene glycol is also a commercially im-
portant raw material for the manufacture of
polyester fibers, chiefly poly(ethylene tere-
phthalate) (! 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), plasti-
cizer, 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 nitrocellu-
lose) [53].
Diethylene Glycol serves as a solvent, soft-
ener (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 mo-
lecular masses find numerous uses in the phar-
maceutical 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
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), pro-
duction 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 ethyl-
ene oxide.
Detailed information about the glycol capac-
ities 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 synthe-
sis gas hitherto still in the experimental phase
are likely to become more important and increas-
ingly 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 conjunc-
tival sac does not affect the rabbit eye [66], but
repeated administration leads to mild conjunc-
tivitis [67]. Ethylene glycol vapor at a concen-
tration of 17 mg/m3 produces ocular damage in
humans [68]. No effects were observed in the
eyes of monkeys exposed to a vapor concentra-
tion 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 concentra-
tion 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 adminis-
tered as an aerosol over a period of several
months.
Human volunteers exposed to maximal con-
centrations of 67 mg/m3 for one month reported
some irritation of the nasal mucous membranes
and occasionally headache. The presence of eth-
ylene glycol in the inhaled atmosphere was per-
ceived at concentrations above 140 mg/m3 [71].
A concentration of 200 mg/m3 was found to be
intolerable [72]. Rats, rabbits, dogs, and mon-
keys 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. Ethyl-
ene 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 carcino-
genic effects were observed. However, typical
formation of oxalate crystals in the kidneys and
other organs was found [78]. Similar experi-
ments 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 ob-
served [81]. Teratogenic and fetotoxic effects
were produced in mice and rats after administra-
tion 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 543

Metabolism. In the body, ethylene glycol is stones is attributed to contamination of the

degraded by alcohol dehydrogenase to form gly-
colaldehyde, 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-hy-
droxy-3-oxoadipate and oxomalate are formed
[83, p. 3827].
11.2. Ethylene Glycol Derivatives
Toxicity data and exposure limits for ethylene
glycols and some monoethylene glycol deriva-
tives are listed in Table 8.
Diethylene Glycol has a low acute oral tox-
icity (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 re-
sulting bladder stones led to the formation of
benign tumors. Production of calcium oxalate
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 fertil-
ity 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].
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 in-
creases [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 Single oral Reference MAK, TLV-TWA,

LD50 in rats, ppm ppm
g/kg

Ethylene glycols
Monoethylene glycol 8 [61] 10 50
Diethylene glycol 20.8 [61] 10
Triethylene glycol 22.1 [61]
Tetraethylene glycol 30.8* [83, p. 3843]
Monoethylene glycol derivatives
Monomethyl ether 3.4 [84] 5 5
(methoxyethanol)
Monomethyl ether acetate 3.93 [61] 5 5
(methoxyethyl acetate)
Monoethyl ether 5.5 [84] 5 5
(ethoxyethanol)
Monoethyl ether acetate 5.1 [61] 5 5
(ethoxyethyl acetate)
Monobutyl ether 2.5 [84] 20 25
(butoxyethanol)
Monobutyl ether acetate 20
(butoxyethyl acetate)
*
mL/kg
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 absorp-
tion decreases markedly as the molecular mass
increases [102104].
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546 Ethylene Glycol
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