Adipic Acid 1

Adipic Acid
Michael Tuttle Musser, E. I. DuPont de Nemours & Co., Sabine River Laboratory, Orange, Texas 77631,
United States

1. Introduction . . . . . . . . . . . . . . . . . 1 7. Storage and Transportation . . . . . . 6

2. Physical Properties . . . . . . . . . . . . 1 8. Derivatives . . . . . . . . . . . . . . . . . . 6
3. Chemical Properties . . . . . . . . . . . 2 8.1. Adiponitrile . . . . . . . . . . . . . . . . . 6
4. Production . . . . . . . . . . . . . . . . . . 2 8.2. Other Derivatives . . . . . . . . . . . . . 7
4.1. Nitric Acid Oxidation of Cyclohexanol 2
9. Uses . . . . . . . . . . . . . . . . . . . . . . 7
4.2. Butadiene-Based Routes . . . . . . . . . 4
4.3. Other Routes . . . . . . . . . . . . . . . . 5 10. Economic Aspects . . . . . . . . . . . . . 8
5. Byproducts . . . . . . . . . . . . . . . . . 5 11. Toxicology and Occupational Health . 8
6. Quality Specifications . . . . . . . . . . . 5 12. References . . . . . . . . . . . . . . . . . . 9

1. Introduction mp, ◦ C 152.1

bp, ◦ C
Adipic acid, hexanedioic acid, 1,4-butan- at 101.3 kPa 337.5
at 13.3 kPa 265
edicarboxylic acid, C6 H10 O4 , M r 146.14, at 2.67 kPa 222
HOOCCH2 CH2 CH2 CH2 COOH [124-04-9], is at 0.67 kPa 191
at 0.133 kPa 159.5
the most commercially important aliphatic di- Relative density (170 ◦ C) 1.085
carboxylic acid. It appears only sparingly in na- Bulk density, kg/m3 600 – 700
ture but is manufactured worldwide on a large Solubility, g/100 g water
at 15 ◦ C 1.42
scale. Its primary application is in the production at 40 ◦ C 4.5
of nylon 66 polyamide, discovered in the early at 60 ◦ C 18.2
at 80 ◦ C 73
1930s by W. H. Carothers of DuPont. Manu- at 100 ◦ C 290
facture of nylon 66 polyamide fiber has grown Dissociation constants
to become one of the dominant processes in the k1 4.6 × 10−5
k2 3.6 × 10−6
synthetic fiber industry. The historical develop- Specific heat of liquid (200 ◦ C), 2.719
ment of adipic acid was reviewed in 1977 [5]. kJ kg−1 K−1
Specific heat of vapor (300 ◦ C), 1.680
kJ kg−1 K−1
Heat of fusion, kJ/kg 115
Heat of vaporization, kJ/kg 549
Heat of solution in water, kJ/kg
2. Physical Properties [6] 10 – 20 ◦ C − 214
90 – 100 ◦ C − 241
Adipic acid is isolated as colorless, odorless Melt viscosity, mPa · s
at 160 ◦ C 4.54
crystals having an acidic taste. It is very solu- at 193 ◦ C 2.64
ble in methanol and ethanol, soluble in water
and acetone, and very slightly soluble in cyclo- Flammability and explosion data are summa-
hexane and benzene. Adipic acid crystallizes as rized in the following:
monoclinic prisms from water, ethyl acetate, or
acetone/petroleum ether. Some physical proper- Closed cup flash point 196 ◦ C
Cleveland open cup flash point 210 ◦ C
ties of adipic acid follow: Autoignition temperature 420 ◦ C
Dust cloud ignition temperature 550 ◦ C
Minimum explosive concentration 0.035 kg/m3
(dust in air)
Minimum cloud ignition energy 600 J
Maximum rate of pressure rise 18.6 MPa/s

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a01 269
2 Adipic Acid
3. Chemical Properties
Adipic acid is stable in air under most con-
ditions, but heating of the molten acid above
230 – 250 ◦ C results in some decarboxylation to
give cyclopentanone [120-92-3], bp 131 ◦ C. The
reaction is markedly catalyzed by salts of metals,
including iron, calcium [7], and barium [8]. The
tendency of adipic acid to form a cyclic anhy-
dride by loss of water is much less pronounced
compared to glutaric or succinic acids [9].
Adipic acid readily reacts at one or both car-
boxylic acid groups to form salts, esters, amides,
nitriles, etc. (Chap. 8). The acid is quite stable
to most oxidizing agents, as evidenced by its
production in nitric acid. However, nitric acid
will attack adipic acid autocatalytically above
180 ◦ C, producing carbon dioxide, water, and
nitrogen oxides.
4. Production
Early commercial processes for manufactur-
ing adipic acid involved a two-step air oxida-
tion of cyclohexane [110-82-7]. Oxidation of
cyclohexane to cyclohexanol – cyclohexanone
at low conversion was followed by a high-
conversion process for air oxidation of the mix-
ture to adipic acid. Currently (2000), however,
all large-scale production is via nitric acid ox-
idation of cyclohexanol [108-93-0], cyclohex-
anone [108-94-1], or a mixture of the two
[ketone – alcohol (KA) oil].
Differences among commercial processes are
mainly in the manufacture of the KA oil. The
six carbon atoms of the adipic acid backbone
usually come from benzene, which is hydro-
genated to cyclohexane, or phenol, which is hy-
drogenated to cyclohexanol. The cyclohexane is
then oxidized with air to KA oil. In the past 20
years, there has been a shift to the lower cost cy-
clohexane-based process [10]. (For KA produc-
tion, see → Cyclohexanol and Cyclohexanone).
Since the early 1980s, a great deal of research
has been carried out on the synthesis of adipic
acid from butadiene and carbon monoxide (Sec-
tion 4.3). However, no commercial plant based
on this technology is currently in operation.
4.1. Nitric Acid Oxidation of
Cyclohexanol
Reaction Mechanism. The second step of
the conventional process, developed by DuPont
in the late 1940s, involves the oxidation of cy-
clohexanol, cyclohexanone, or a mixture of both
with nitric acid [11], [12]. Adipic acid is ob-
tained in greater than 90 % yield. Major byprod-
ucts are carbon dioxide, nitrogen oxides, and
some lower molecular mass dicarboxylic acids.
Some byproducts arising from impurities in the
starting KA oil are also present.
The chemical mechanism was discussed orig-
inally in 1956 [13] and later in greater detail
[14], [15]. The latter reports include kinetic and
reactor design considerations. Results of related
studies, especially on the later stages of the re-
action, were published at about the same time
[16–18]. A summary of the findings of these in-
vestigations is given in Figure 1.
Cyclohexanol (1) is oxidized to cyclohex-
anone (2), accompanied by generation of ni-
trous acid. The cyclohexanone then reacts by
one of three possible pathways leading to
the formation of adipic acid (8). The ma-
jor fraction of the reaction occurs via nitro-
sation to produce 2-nitrosocyclohexanone (3),
then by further reaction with nitric acid to
form the 2-nitro-2-nitrosoketone (6). Hydrolytic
cleavage of this intermediate gives 6-nitro-6-
hydroximinohexanoic acid, also known as ni-
trolic acid (9). This breaks down further to give
adipic acid and nitrous oxide, the main unre-
covered nitric acid reduction products. Typically
2.0 mol of nitric acid is converted to nitrous
oxide for each mole of adipic acid produced.
The second pathway occurs at higher tem-
perature, where nitration predominates. At these
elevated temperatures, the pathway via the dini-
troketone (4) becomes significant.
The third path proposed by the early investi-
gators involves the intermediate formation of the
1,2-diketone (5) or its dimer. Conversion of this
material to adipic acid in good yield requires the
use of a vanadium catalyst. The effect of vana-
dium on the overall yield suggests a significant
contribution by this pathway.
The intermediate nitrosoketone (3) can un-
dergo two important side reactions. Multiple ni-
trosation leads to the intermediate (10), which
loses carbon dioxide to produce glutaric acid
 Adipic Acid 3

Figure 1. Reaction paths in nitric acid oxidation of cyclohexanol

(11) or succinic acid from subsequent reaction in a continuously circulated loop of nitric acid
with nitric acid. Copper metal is added to the ni- mother liquor (NML) that passes through the en-
tric acid to inhibit these reactions. In systems tire system, as shown by the bold line.
containing a relatively high steady-state con-
centration of the nitrosoketone (3) or the tau-
tomeric oximinoketone, a Beckmann-type rear-
rangement leads to 5-cyanopentanoic acid (12)
in minor amounts. This material is slowly hy-
drolyzed to adipic acid.

Commercial Nitric Acid Oxidation Pro-

cesses. The basic technology for carrying out
the nitric acid oxidation of cyclohexanol – cyclo-
hexanone (KA) remains similar to that described
in the early patent literature. Advances have cen-
tered on improvement in byproduct removal,
catalyst and nitric acid recovery, and suppression
of nitrous oxide, a greenhouse gas which was
traditionally vented to the atmosphere. Because Figure 2. Flow diagram of a process for nitric acid oxida-
of the corrosive nature of nitric acid, plants are tion of cyclohexanone – cyclohexanol
constructed of stainless steel (type 304L or bet- a) Reactor; b) Cleanup reactor; c) NOx bleacher; d) Nitric
ter), or of titanium in areas of most severe expo- acid absorber; e) Concentrator; f) Crystallizer; g) Filter or
centrifuge; h) Dryer; i) Cooler
sure. The block flow diagram in Figure 2 shows
a typical layout for a commercial nitric oxida- The reactor (a) is essentially a large
tion process [5], [19]. The reaction is carried out heat exchanger, controlled at 60 – 80 ◦ C and
4 Adipic Acid
0.1 – 0.4 MPa. To this is fed the recycled
NML, the KA feed material, the makeup
acid containing 50 – 60 % nitric acid and the
copper – vanadium catalyst [20], [21]. Resi-
dence time in (a) is less than 5 min. In some facil-
ities, the effluent is passed through a second re-
actor (b) at elevated temperature (110 – 120 ◦ C)
[22]. This high-temperature converter (b) can
be used to complete the reaction and reduce
the amount of impurities which need to be re-
moved through crystallization. The reaction is
very exothermic (6280 kJ/kg) and normal heat-
exchanger surfaces tend to frost, leading to loss
of temperature control. Several different reactor
designs have been patented which aid in remov-
ing the heat of reaction and minimizing energy
usage in the process [23–28]. An excess of re-
cycled NML to KA feed stream of at least 3 : 1
and up to 1000 : 1 is maintained to control the
reaction and improve the yield [21].
The product stream is passed through a
bleacher (c), in which excess dissolved nitro-
gen oxides are removed with air and sent to
the absorber (d), where they are reabsorbed and
recovered as nitric acid. The off-gas from the
absorber can be used to initiate the oxidation
at lower temperatures by passing it through the
KA feed stream before it is fed to the oxidizer
[29–31]. Removal of the NOx from the off-gas
by scrubbing with KA has also been described
[32]. The water produced in the process is then
removed in a concentrating still (e) that is usu-
ally operated under vacuum. The concentrated
product stream is either recycled to the reactor
with diversion of a portion to product recovery
or passed to product recovery prior to recycle of
the NML filtrate. Crude adipic acid is removed
from the NML loop by crystallization (f) fol-
lowed by subsequent filtration or centrifugation
(g) [33–35]. A portion of this effluent stream,
which contains high concentrations of glutaric
acid, succinic acid, and byproducts, is processed
to recover the vanadium and copper catalysts and
remove the byproduct acids. Metal recovery is
usually accomplished by ion exchange [36]. The
crude adipic acid from the first crystallizer (g)
is dissolved and recrystallized at least one addi-
tional time before proceeding to a dryer (h) and
a cooler (i). If the adipic acid is not needed in
dry form, the crystals from the centrifuge/filter
(g) can be dissolved in water and added to a so-
lution of aqueous 1,6-hexanediamine to make
nylon salt.
Other improvements of the conventional pro-
cess have been described [37], especially in con-
nection with separation and recovery of the diba-
sic acid byproducts [38–41]. The crude adipic
acid is refined to varying degrees, depending
upon the end use, but usually is recrystallized
from water. Destruction of impurities by reflux-
ing in 60 % nitric acid containing dissolved
vanadium has been claimed to produce high-
quality product [42].
4.2. Butadiene-Based Routes
In the early 1970s, BASF began an extensive re-
search program on producing dimethyl adipate,
a diester that could be hydrolyzed to adipic acid.
The process involved carbomethoxylation of bu-
tadiene with carbon monoxide and methanol to
give methyl 3-pentenoate using a cobalt catalyst
and pyridine at high-pressure [43]. The methyl
3-pentenoate was then separated from byprod-
ucts by distillation. The second carbomethoxy-
lation to give dimethyl adipate occurs at lower
pressure but requires a lower pyridine to cobalt
ratio [44]. The hydrolysis of the diester to adipic
acid and methanol is a high-yield catalytic pro-
cess [45]. The overall yield from butadiene ap-
pears to be about 70 %. It is believed this process
has been demonstrated on a pilot-plant scale, but
not yet commercialized.
In the mid-1980s, DuPont also began a major
program on a butadiene-based route. In contrast
to the BASF diester route, it involved the direct
dihydrocarboxylation of butadiene to adipic acid
(Fig. 3). The first step [46], which can be cat-
alyzed by palladium, rhodium, or iridium, leads
to largely 3-pentenoic acid (12). The second
step [47], catalyzed by rhodium or iridium gives
adipic acid (13), 2-methylglutaric acid (14), and
2-ethylsuccinic acid (15). The advantage of this
process was that the 2-methylglutaric and 2-
ethylsuccinic acids could be isomerized to adipic
acid by the same catalyst system [48]. The cata-
lyst seems to require a halide promoter, such as
hydroiodic acid. The solvent for this process is
usually a saturated carboxylic acid, such as pen-
tanoic acid, which is a byproduct of the process.
Since the late 1980s most major chemical com-

panies have issued numerous patents on varia-
tions of these butadiene based routes [49–51].
Figure 3. Hydrocarboxylation of butadiene to adipic acid
4.3. Other Routes
In addition to the commercial two-step air/nitric
acid oxidation of cyclohexane and the carboxy-
lation/carbomethoxylation of butadiene, sev-
eral other processes have been investigated.
Research at Monsanto on palladium halide
catalyzed dicarbonylation of 1,4-disubstituted
2-butenes was reported in early 1984 [52].
This process produces adipic acid from 1,4-
dimethoxy-2-butene, carbon monoxide, and pal-
ladium chloride at 100 ◦ C after the resulting un-
saturated dimethyl ester has been hydrogenated
and hydrolyzed.
The one-step oxidation of cyclohexane with
nitric acid [53], [54], nitrogen dioxide [55], or
air has been described. The one-step all-air ox-
idation of cyclohexane is economically very at-
tractive and has been heavily researched. Early
work was performed by Gulf Research and De-
velopment [56–58], Asahi Chemical Industries
[59], [60], and others [61]. For example, cyclo-
hexane is oxidized in one step to adipic acid in
70 – 75 % yield, in the presence of a cobalt ac-
etate catalyst in acetic acid as solvent [59]. More
recently, there has been renewed interest in this
work, and several patents have been issued to
Redox Corporation and Bayer. [62–65].
Adipic acid can be produced by ozonolysis of
cyclohexene [66] or by addition of a carboxylic
Adipic Acid 5
acid to cyclohexene and subsequent oxidation
of the resulting ester with nitric acid [67]. For-
mation of adipic acid derivatives by electrolytic
coupling of acrylates has also been described
[68].
5. Byproducts
The major byproducts of nitric acid oxidation
of KA are glutaric acid [110-94-1] and succinic
acid [110-15-6], and minor amounts of pen-
tanoic acid and hexanoic acid are also formed. In
commercial operations, the nitric acid reaction
medium (NML) contains high concentrations of
glutaric and succinic acids, resulting from the
recycling of the mother liquor after crystalliza-
tion of the adipic acid. A portion of this stream is
diverted and processed separately to remove the
byproduct acids and recover nitric acid and the
copper and vanadium catalysts. Early commer-
cial processes discarded these byproduct acids.
However, most companies now recover these
acids either as a mixture of dibasic acids (DBA)
or convert them to dibasic esters (DBE) for a
variety of uses.
Following the removal of the copper and
vanadium by ion exchange and distillation of
the nitric acid in water, methanol can be added
to convert the acids to their methyl esters. Then
the esters are distilled to give a mixture or the
individual esters [69–71].
Sometimes the acids are removed by distil-
lation to produce a mixture of acids and anhy-
drides, especially glutaric anhydride [108-55-4]
and succinic acid [108-30-5] [72–76]. Separa-
tion of the individual acids by crystallization
and extraction with organic solvents has been
described [77], [78]. Other means of separat-
ing the byproduct acids include addition of in-
organic salts [79], a C1 – C6 primary alkylamine
[80], or urea [81], and extraction by a ketone
solvent [82].
6. Quality Specifications
Commercial adipic acid is one of the purest
large-scale manufactured chemicals because of
the stringent requirements of its major con-
sumer, the synthetic fibers industry. The U.S.
6 Adipic Acid
FDA has approved adipic acid as a food additive.
Because essentially all adipic acid manufactur-
ers use a nitric acid oxidation process, impurities
are similar. Purity is affected mostly by varia-
tions in the synthesis of the KA intermediate
and in the extent of adipic acid recrystallization
and purification. Some typical specifications for
food-grade adipic acid are: color, APHA equiva-
lence (Hazen) 10 max., water 0.2 % max., ash on
ignition 10 ppm max., iron 1.0 ppm max., adipic
acid content 99.6 % min. [83].
Procedures for analysis of food-grade adipic
acid are described in [84]. General methods for
water (Karl Fischer), color in methanol solutions
(APHA), iron, and other metallic impurities in
commercial acid have been summarized [85].
Resin-grade adipic acid frequently has limits for
succinic (ca. 50 ppm) and caproic (ca. 30 ppm)
acids, and for hydrocarbon oils (ca. 15 ppm).
Carboxylic acids can be determined by gas chro-
matography of their esters or by liquid chro-
matography of the free acids [86]. Total nitro-
gen can be determined by chemical reduction
and distillation of ammonia from an alkaline so-
lution. Hydrocarbon oil may be determined by
IR analysis of a halocarbon extract of a solution
of the salt.
7. Storage and Transportation
Adipic acid is conveyed pneumatically or me-
chanically from the drying equipment to the stor-
age or shipping container. These containers may
be aluminum or stainless steel railroad hopper
cars, trucks, plastic bags, or drums. Principal
hazards in handling adipic acid are the danger
of dust explosion and skin or mucus membrane
irritation on exposure to the dust. Particle size
control and flow characteristics are also impor-
tant factors due to the tendency of adipic acid
that contains excessive fines to cake during stor-
age.
8. Derivatives
8.1. Adiponitrile
The most important derivative of adipic
acid is adiponitrile, 1,6-hexanedinitrile, 1,4-
dicyanobutane, [111-69-3], M r 108.14, bp
298 – 300 ◦ C (at 101.3 kPa), 154 ◦ C (at 1.3 kPa),
fp 2.4 ◦ C, n25 25
D 1.4370, d 4 0.9599, an inter-
mediate in the manufacture of the other major
nylon 66 component, 1,6-hexanediamine. The
original production process involved conversion
of the acid to the dinitrile by liquid- [87] or
vapor-phase dehydration [88] of the ammonium
salt in the presence of phosphoric acid or a
boron – phosphorus catalyst. Although this was
the predominate technology used for adiponi-
trile production in the past, it is no longer used
by any major nylon 66 producers.
Other routes which have been used include a
process by Celanese, which in the 1960s and
1970s avoided manufacturing adiponitrile by
producing 1,6-hexanediamine from ammonoly-
sis of 1,6-hexanediol, which in turn was made
by the hydrogenation of adipic acid [89]. This
adipic acid based route was shut down around
1980. In 1948, DuPont introduced, and for sev-
eral years operated, a process based on furfural
[90]. From 1951 to 1983, DuPont operated a bu-
tadiene chlorination process [91]. The interme-
diate 1,4-dichloro-2-butene was converted to 3-
hexenedinitrile with sodium cyanide and then
hydrogenated to adiponitrile. Current adiponi-
trile manufacture is based on either propylene
or direct hydrocyanation of butadiene.
In 1965 Monsanto introduced a process in-
volving the electrolytic coupling of acrylonitrile
[92]. This process, or variations of it, is also used
in the United Kingdom and Japan. DuPont be-
gan the direct hydrocyanation of butadiene in
1972 [93]. Now all DuPont adiponitrile pro-
duction, including a joint venture with Rhône-
Poulenc (now Rhodia) in France, uses this tech-
nology. The process consists of a two step hy-
drocyanation, catalyzed by a nickel(0) phos-
phite complex and promoted by certain Lewis
acids [94–96]. The mixture of isomeric pente-
nenitriles and methylbutenenitriles produced in
the first step is isomerized to predominately 3-
and 4-pentenenitrile [97–99]. Subsequent anti-
Markovnikov addition of hydrogen cyanide to
the pentenenitriles produces adiponitrile.
Other routes that have been revealed in-
clude chemical dimerization of acrylonitrile to
3-hexenedinitrile [100–102] and hydrocyana-
tion of butadiene with a copper halide cata-
lyst to yield 3-pentenenitrile [103], followed
by disproportionation to dicyanobutenes and
 Adipic Acid 7

butenes. Finally, another dimerization route to molecular mass polyester polyols having hy-
adiponitrile involves the addition of acryloni- droxyl end groups are used with polyisocyanates
trile to 2-methyleneglutaronitrile in the presence to produce polyurethane resins.
of zinc or cobalt complexes and a Lewis base
Table 1. Boiling points of adipic acid esters
[104]. The dimer is then hydrocyanated to 1,2,4-
butanetricarbonitrile followed by dehydrocya- Ester p, kPa bp, ◦ C
nation to 3-hexenedinitrile [105].
Monomethyl [627-91-8] 1.3 158
Dimethyl [627-93-0] 1.7 115
Monoethyl [626-86-8] 0.9 160
Diethyl [141-28-6] 1.7 127
8.2. Other Derivatives Di-n-propyl [106-19-4] 1.5 151
Di-n-butyl [105-99-7] 1.3 165
Di-2-ethylhexyl [103-23-1] 0.67 214
Salts. Adipic acid forms alkali metal and am- Di-n-nonyl [151-32-6] 0.67 230
monium salts that are water-soluble and alka- Di-n-decyl [105-97-5] 0.67 244
line earth salts that are only moderately soluble.
Their solubilities in 100 g of water are: diammo-
nium salt [3385-41-9] 40 g (14 ◦ C), disodium Anhydrides. The usual form of the anhy-
salt [7486-38-6] 59 g of hemihydrate (14 ◦ C), dride produced by dehydrating adipic acid is the
dipotassium salt [19147-16-1] 65 g (15 ◦ C), cal- linear, polymeric form [2035-75-8]. Distillation
cium salt [22322-28-7] 4 g of monohydrate of the polymeric anhydride is said to produce the
[18850-78-7] (13 ◦ C), 1 g of anhydrous salt monomeric cyclic form, which is very unstable
(100 ◦ C). and reverts readily to the linear, polymeric an-
The most common salt is poly(1,6- hydride.
hexanediammonium hexanedioate), produced
by interaction of adipic acid with 1,6- Amide. The diamide, C6 H12 N2 O2
hexanediamine. This water-soluble salt, the pre- [628-94-4], mp 228 ◦ C, is practically insoluble
cursor to nylon 66, is readily shipped or stored in cold water. It has been traditionally prepared
prior to the final polyamidation, which occurs from the dimethyl ester by treatment with con-
with the removal of water. The chemistry of this centrated ammonium hydroxide or by heating
step has been reviewed [106]. the diammonium salt of adipic acid in a stream
of ammonia. Other substituted amides can be
Esters and Polyesters. The esters and prepared from amines by the usual synthetic
polyesters of adipic acid constitute the largest methods.
non-polyamide market for adipic acid. Esters
made from long-chain alcohols are used as
plasticizers and lubricants, while those from 9. Uses
short-chain alcohols are used primarily as sol-
vents. Refluxing adipic acid with methanol in About 80 % of worldwide adipic acid consump-
the presence of an acid catalyst can produce tion is used for the manufacture of nylon 66
monomethyl adipate, along with the diester. fibers and resins. This is down from about 87 %
Electrolysis of the salt of the monoester (Kolbe in 1981. Table 2 summarizes consumption in
synthesis) produces dimethyl sebacate, another three major regions of the world. A small amount
polyamide precursor. The boiling points of some of adipic acid is still used captively to produce
esters are listed in Table 1. The esters dissolve adiponitrile.
readily in most organic solvents. While dimethyl Large amounts are converted to esters for
adipate is the most commonly used solvent, di- use in plasticizers, lubricants and in a variety
2-ethylhexyl adipate is the most widely used of polyurethane resins. The monomeric esters
plasticizer. Other simple adipate plasticizers in- are important plasticizers for poly(vinyl chlo-
clude the n-octyl, n-decyl, isodecyl, and isooctyl ride) and other resins, while polymeric esters
esters. More complex polymeric plasticizers, are used when unusually high plasticizer lev-
prepared from glycols, account for a little less els are required. Polyurethane resins employing
than half the adipic acid based plasticizers. Low adipic acid are produced from polyisocyanates
and polyester polyols (adipates). These are used
8 Adipic Acid
Table 3. Worldwide adipic acid capacity as of January 1999 [113]
in specialty foams, lacquers, adhesives, surface
coatings and spandex fibers for stretch-wear. Region Capacity, 103 t/a Major producers
(capacity, 103 t/a)
3
Table 2. Adipic acid consumption, 10 t/a [107–110]
North America 1058 DuPont (740), Solutia
United States Western Europe Japan (295), Allied (23)
Western Europe 841 Rhodia (280), BASF
1991 1995 1991 1995 1991 1995 (260), DuPont (220),
Bayer (55), Radici
Nylon 66 611 629 267 225 35 34 (60), UCB
fiber Far East 70 Asahi (120), DuPont
Nylon 66 115 193 86 110 23 26 (115), China (139),
resin Korea (70)
Plasticizers 30 38 21 24 13 14 Others 115
Polyurethane 38 39 28 45 18 13
resins
Miscellaneous 17 23 66 88 19 17
Production. Adipic acid production is dom-
Adipic acid is added to gelatins and jams as inated by nylon 66 fiber and resin manufacture;
an acidulant and to other foods as a buffering as a result, the economic picture for the acid
or neutralizing agent. It is also used to mod- is strongly dominated by the markets for these
ify the properties of unsaturated polyesters for materials. Less than 15 % of U.S. production
use in reinforced plastics and alkyd coatings. is sold on the merchant market, essentially for
Polyamide – epichlorohydrin resins employing non-nylon uses. This ratio is higher in Western
adipic acid are used to increase the wet strength Europe and Japan. The synthesis of adiponi-
of paper products. Other miscellaneous appli- trile from adipic acid, once significant, is no
cations are in the adhesives, insecticide, tanning longer used by any major manufacturers. How-
and dying, and textile industries. Adipic acid and ever, it continues to a very limited degree in some
mixed dibasic acids (DBAs) are being used as Eastern European countries. The non-nylon uses
buffers in flue gas desulfurization treatment in for adipic acid have grown at about 6 % per
power plants [111]. year since 1970. Production costs closely paral-
lel raw material prices (cyclohexane and ammo-
nia), which in the late 1990s have fallen with the
10. Economic Aspects decline in crude oil prices. The largest growth
rate for adipic acid, as well as nylon 66, is in
Capacities. Total worldwide annual capac- China and the Far East. The projected growth
ity for adipic acid was 2.5 × 106 t/a in 1999 (Ta- rate in the United States and Western Europe
ble 3). Although this reflects only a 15 % growth is expected to be slow, so the supply/demand
in capacity since 1980, it also reflects the shut- picture should remain relatively constant for the
ting down of several adiponitrile plants which next few years.
had used adipic acid as a starting material, thus
making it available for other uses. The North
American capacity was 1.06 × 106 t/a, or 42 % 11. Toxicology and Occupational
of the total, whereas Western Europe accounted Health
for 35 %, produced mainly by the United King-
dom, France, Germany and Italy. Imports and Adipic acid is a minor irritant of low oral tox-
exports have become significant. In 1995 U.S. icity. The lowest published lethal dose (LDLo)
exports were 71 × 103 t [112] or 8.5 % of U.S. is 3600 mg/kg (rat, oral), LD50 275 mg/kg (rat
consumption. This is up from 1.2 % in 1979 or mouse, i.p.), LD50 1900 mg/kg (mouse, oral)
[113]. Since 1970, U.S. consumption of adipic [114]. Some delayed body weight increases and
acid has increased by 80 %, or about 3 % per changes in certain enzymes and in urea and chlo-
year. Growth rates are expected to remain at ride level in the blood were observed in chronic
about 3 % per year through 2000. Regional ca- feeding tests [115]. No teratogenic activity was
pacities are shown in Table 3, along with annual detected in studies with pregnant mice [116].
capacities for the major producing companies. In metabolism studies with rats fed 14 C-labeled
 Adipic Acid 9

adipic acid, both unchanged adipic acid and nor- 7. W. Hentzchel, J. Wislicenus, Liebigs Ann.
mal metabolic products were detected in the Chem. 275 (1983) 312.
urine [117], [118]. 8. G. Vavon, A. Apchie, Bull. Soc. Chim. Fr. 43
Exposure of the mucous membranes (eyes, (1928) 667.
respiratory tract) produces irritation; prolonged 9. J. W. Hill, J. Am. Chem. Soc. 52 (1930) 4110.
exposure to the skin can be drying or irritating. In 10. W. F Stahl: “Organic Chemicals A-A1,” in
case of spills or leaks, personnel should be pro- Chemical Economics Handbook , SRI
tected from inhalation or excessive skin contact. International, Menlo Park, Calif., 1996,
608.5000G
Dusting should be controlled and static sparks
11. DuPont, US 2 557 282, 1951 (C. Hamblett, A.
should be avoided. Water may be used to flush MacAlevy).
the area. 12. DuPont, US 2 703 331, 1953 (M. Goldbeck, F.
Although no TLV or MAK has been estab- Johnson).
lished, the airborne exposure should be less than 13. H. Godt, J. Quinn, J. Am. Chem. Soc. 78
that of an organic nuisance dust: ACGIH (1979) (1956) 1461 – 1464.
8-h TWA 10 mg/m3 (total dust) and 8-h TWA 14. D. van Asselt, W. van Krevelen, Recl. Trav.
5 mg/ m3 (respirable dust) (OSHA TLV is 15 Chim. Pays Bas 82 (1963) 51 – 56, 429 – 437,
mg/ m3 for total dust). Toxicity data from rep- 438 – 449.
resentative types of adipic acid derivatives are 15. D. van Asselt, W. van Krevelen, Chem. Eng.
shown in Table 4. Sci. 18 (1963) 471 – 483.
16. I. Y. Lubyanitskii, R. Minati, M. Furman,
Table 4. Toxicity data for adipic acid derivatives [119]
Russ. J. Phys. Chem. (Engl. Transl.) 32 (1962)
Derivative Oral LD50 Inhalation Other LD50 , mg/kg 294 – 297.
(rat) mg/kg LC50 (rat, 17. I. Y. Lubyanitskii, Zh. Obshch. Khim. 36
3
4 h), mg/m
(1962) 3431
Adiponitrile 300 1710 50 (guinea pig, 18. I. Y. Lubyanitskii, Zh. Prikl. Khim.
s.c.) (Leningrad) 36 (1963) 819 – 823.
Di-2-ethylhexyl 9110 – 900 (rat, i.v.)
adipate
19. Ullmann, 5th ed., A1, 271.
Dimethyl – – 1809 (rat, i.p.) 20. BASF, US 3 564 051, 1971 (E. Haarer, G.
adipate Wenner).
Adipamide 500
Magnesium – – 180 (mouse, i.v.)
21. BASF, GB 1 092 603, 1969 (G. Riegelbauer,
adipate A. Wegerich, A. Kuerzinger, E. Haarer).
22. DuPont, US 3 359 308, 1967 (O. Sampson)
23. ICI, US 3 754 024, 1973 (F. Foster, P. Hay).
24. ICI, US 3 950 410, 1976 (J. Lopez-Merono).
25. ICI, US 3 997 601, 1976 (P. Langley).
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6. Ullmann 5th ed. A1, 259. D. Danly).
10 Adipic Acid
37. Celanese, US 3 965 164, 1976 (J. Blay).
38. Celanese, US 3 983 208, 1976 (J. Blay).
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40. ICI, GB 1 480 480, 1977 (A. Bowman).
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56. Gulf R & D, US 3 231 608, 1966.
57. Gulf R & D, US 4 032 569, 1977 (A.
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63. Bayer & Redox, US 5 463 119, 1995 (J.
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65. Bayer, DE 4 428 977, 1996 (C. Casser, K.
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68. Monsanto, GB 1 447 772, 1976 (C. Campbell,
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69. El Paso Products Co., US 4 316 775, 1982 (W.
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70. El Paso Products Co., DE 3 043 051, 1982 (N.
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71. DuPont, US 3 991 100, 1976 (S. Hochberg).
72. ICI, US 4 191 616, 1980 (B. Baker).
73. Allied Chem., FR 1 347 525, 1963 (J. Benfield,
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74. ICI, US 3 511 757, 1970 (W. Costain, B.
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75. BASF, US 3 564 051, 1971 (E. Haarer, G.
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76. DuPont, CA 707 340, 1965.
77. DuPont, US 3 338 959, 1967 (C. Sciance, L.
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78. Monsanto, US 3 329 712, 1967 (D. Danly, G.
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79. Asahi, JP-Kokai 115 314, 1979 (J. Nishikido,
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80. BASF, DE 3 002 256, 1981 (W. Rebofka, G.
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81. Asahi, US 4 146 730, 1979 (J. Nishikido).
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89. Celanese, FR 1 509 288, 1968 (P. Volpe, W.
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90. J. Hardy in H. Simonds, J. Church (eds.): The
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95. DuPont, US 3 496 218, 1970 (W. Drinkard).
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98. DuPont, US 3 536 748, 1970 (W. Drinkard, R.
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99. DuPont, US 3 542 847, 1970 (W. Drinkard, R.
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100. ICI, US 4 138 428, 1979 (J. Jennings, P.
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Adiponitrile → Adipic Acid
Adipic Acid 11
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