Acrylic Acid and Derivatives : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience

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Takashi Ohara1, Takahisa Sato2, Noboru Shimizu3, Gnter Prescher4, Print this page
Helmut Schwind5, Otto Weiberg6, Klaus Marten7, Helmut Greim8 SEARCH THIS TITLE
1Nippon Shokubai Kagaku Kogyo Co., Ltd., Osaka, Japan
2Nippon Shokubai Kagaku Kogyo Co., Ltd., Osaka, Japan
3Nippon Shokubai Kagaku Kogyo Co., Ltd., Osaka, Japan Advanced Product Search
4Degussa AG, Zweigniederlassung Wolfgang, Hanau, Federal
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5Degussa AG, Zweigniederlassung Wolfgang, Hanau, Federal
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6Degussa AG, Zweigniederlassung Wolfgang, Hanau, Federal
Republic of Germany
7Sichel-Werke GmbH, Hannover, Federal Republic of Germany
8Institut fr Toxikologie und Umwelthygiene, TU Mnchen, Freising-
Weihenstephan, Federal Republic of Germany

Copyright 2003 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights
reserved.
DOI: 10.1002/14356007.a01_161.pub2
Article Online Posting Date: March 15, 2003

Abstract | Full Text: HTML

Abstract
The article contains sections titled:

1. Acrylic Acid and Esters

1.1. Physical Properties
1.2. Chemical Properties
1.3. Production
1.3.1. Propene Oxidation
1.3.2. Esterification
1.4. Quality Specifications and Analysis
1.5. Storage and Transportation
1.6. Uses
1.7. Some Special Acrylates
1.8. Economic Aspects
1.9. Toxicology and Occupational Health
2. Cyanoacrylates
3. Acrylamide

[Top of Page]

1. Acrylic Acid and Esters

Acrylic acid [79-10-7], 2-propenoic acid, CH2=CHCOOH, and its esters CH2=CHCOOR, which are also known as acrylates,
are flammable, volatile, mildly toxic, colorless liquids. Hydroquinone or its monomethyl ether is usually added to commercial
preparations to inhibit polymerization. Formerly, acrylic acid and acrylates were produced industrially via a variety of routes
such as acrylonitrile hydrolysis and the modified Reppe process (see Section Production). However, remarkable progress on
the catalytic oxidation of propene to acrylic acid via acrolein has led to almost complete replacement of these earlier
processes.

Esters such as methyl, ethyl, n-butyl, and 2-ethylhexyl acrylates, as well as acrylic acid, are in worldwide use, primarily for
polymers. Other esters, including multifunctional acrylates, are produced for special applications.

Chemically, acrylamide (see Chap. Acrylamide) is a derivative of acrylic acid but the amide is produced by hydration of
acrylonitrile instead of by amidation of the acid.

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Acrylic Acid and Derivatives : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScience
1.1. Physical Properties
Acrylic Acid is a clear, colorless liquid, bp 141.0 C (101.3 kPa), mp 13.5 C; it forms crystalline needles in the solid state.
Other important physical constants are listed below [1-6]:

Mr 72.06
Refractive index
Density 1.060 (10 C), 1.040 (30 C), 1.018 (50 C) g/cm3
Viscosity at 25 C 1.149 mPa s
Critical temperature 380 C
Critical pressure 5.06 MPa
Heat of vaporization at 101.3 kPa 45.6 kJ/mol
Heat of combustion 1376 kJ/mol
Heat of melting at 13 C 11.1 kJ/mol
Heat of neutralization 58.2 kJ/mol
Heat of polymerization 77.5 kJ/mol
Dissociation constant at 25 C 5.5 105; pK = 4.26 a

Vapor pressure as function of temperature:

t, C 0 20 40 60 100 120 141

p, kPa 0.31 1.03 2.93 7.2 33.2 63.3 101.3

Acrylic acid is highly miscible with water, alcohols, esters, and many other organic solvents. Figure 1 gives the density of the
aqueous solution as a function of water content. Table 1 shows the freezing points of various acetic acid acrylic acid and
water acrylic acid solutions.

Table 1. Freezing points of acrylic acid mixtures: A with acetic acid, B with water

System A, wt % acetic acid Freezing point,C System B, wt % water Freezing point, C [5]

0 13.5 0 13.5
10 7.5 5 5.5
20 0.7 10 1.0
40 14.1 20 5.5
50 23.5 30 10.3
50.2 23.8 37 12.5
60 13.4 40 12.0
80 3.7 60 8.0
100 16.6 80 4.0
100 0

Figure 1. Relationship between density of aqueous acrylic acid solution and water content

Derivatives. Table 2 lists physical properties of representative derivatives other than esters, Table 3 those of five commercial
acrylates, and Table 4 those of other acrylates including some diesters.

Table 2. Physical properties of acrylic acid derivatives

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Acrylic anhydride Acryloyl chloride Acrylamide

CAS registry number [2051-76-5] [814-68-6] [79-06-1]

Structural formula (CH2 = CHCO)2O CH2 = CHCOCl CH2 = CHCONH2
Molecular formula C 6 H 6 O3 C3H3ClO C3H5NO
Mr 126.11 90.51 71.08
mp, C 84.5
bp, C/p in kPa 38/0.27 75/101 125/16.6
Density, g/cm3 1.113 (20 C) 1.122 (30 C)
Refractive index, 1.4487 1.4337

Table 3. Physical properties of the most important acrylates

Property Methyl Ethyl n-Butyl Isobutyl 2-Ethylhexyl

acrylate acrylate acrylate acrylate acrylate

CAS registry number [96-33-3] [140-88-5] [141-32-2] [106-63-8] [103-11-7]

Molecular formula C4H6O2 C5H8O2 C7H12O2 C7H12O2 C11H20O2
Mr 86.09 100.12 128.17 128.17 184.28
mp, C 76 72 64.6 61 90
bp at 101.3 kPa, C 80.3 99.4 147.4 138 216
Specific heat (l), 0.48 0.47 0.46 0.46 0.46
kJ mol1 K1
Solubility at 25 C
in water (g/100 g) 5 1.5 0.2 0.2 0.01

of water in ester 2.5 1.5 0.7 0.6 0.15

(g/100 g)
Azeotropes
with water, bp, C 71 81.1 94.5

water content, wt % 7.2 15 40

with methanol, bp, 62.5 64.5

C
methanol content, 54 84.4
wt %
with ethanol, bp, C 73.5 77.5

ethanol content, 42.4 72.5

wt %
with n-butanol, bp, 119
C
n-butanol content, wt % 89
Heat of vaporization at 33.2 34.8 36.5 38.1 47.0
bp, kJ/mol
Heat of polymerization, 84.7 77.9 77.3 60.1
kJ/kg
Vapor pressure, kPa
at 0 C 4.2 1.2 0.14

at 20 C 9.3 3.9 0.44

at 50 C 35.9 17.3 2.82 0.16

at 100 C 21.9 2.1

at 150 C 14.6
Refractive index, 1.4040 1.4068 1.4190 1.4150 1.4365
Relative density, 0.9535 0.8998 0.8852
0.9565 0.9231 0.9015 0.890 0.8869

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Viscosity, mPa s
at 20 C 0.53 0.69 0.90 0.78 1.7

at 25 C 0.49 0.55 0.81 1.54

at 40 C 0.50 0.70 1.2

Autoignition 393 355 267 340 230
temperature, C
Flammability range in 2.8 25 1.8 1.5 9.9 1.9 8.0 0.6 1.8
air, vol % saturated
Flash point
closed cup, C 3 9 41 33 87

open cup, C 2 19 47 92

Table 4. Physical properties of acrylic esters and diesters

Ester CAS Molecular Mr bp, C / Refractive Relative

registry formula p, kPa index, density,
number

n-Propyl [925-60-0] C6H10O2 114.15 44/5.3 1.4130 0.9078

n-Pentyl [2998-23-4] C8H14O2 142.20 48/0.9 1.4240 0.8920
n-Hexyl [2499-95-8] C9H16O2 156.23 40/0.2 1.4280 0.8882
n-Heptyl [2499-58-3] C10H18O2 170.25 57/0.1 1.4311 0.8846
Isopropyl [689-12-3] C6H10O2 114.15 52/14 1.4060 0.8932
sec-Butyl [2998-08-5] C7H12O2 128.17 60/6.7 1.4140 0.8914
tert-Butyl [1663-39-4] C7H12O2 128.17 120/101.3 1.408 0.879
Allyl [999-55-3] C6H8O2 112.13 47/5.3 1.4320 0.9441
2-Hydroxyethyl [818-61-1] C5H8O3 116.12 74/0.7 1.4505 1.1038 (25 C)
2-Hydroxypropyl [999-61-1] C6H10O3 130.14 77/0.7 1.4443 1.5036
Ethylene glycol diester [2274-11-5] C8H10O4 170.17 70/0.1 1.4529
1,2-Propanediol diester [25151-33-1] C9H12O4 184.19 60/0.04 1.4470
1.4-Butanediol diester [31442-13-4] C10H14O4 198.22 83/0.1 1.4538

1.2. Chemical Properties

Acrylic acid and its esters undergo reactions characteristic of both unsaturated compounds and aliphatic carboxylic acids or
esters. The high reactivity of these compounds stems from the two unsaturated centers situated in a conjugated position. The
carbon atom, polarized by the carbonyl group, behaves as an electrophile; this favors the addition of a large variety of
nucleophiles and active hydrogen compounds to the vinyl group. Moreover, the carbon-carbon double bond undergoes
radical-initiated addition reactions, DielsAlder reactions with dienes, and polymerization reactions.

The carboxyl function is subject to the displacement reactions typical of aliphatic acids and esters, such as esterification and
transesterification.

Joint reactions of the vinyl and carboxyl functions, especially with bifunctional reagents, often constitute convenient routes to
polycyclic and heterocyclic substances.

Acrylic acid and its esters polymerize very easily. The polymerization is catalyzed by heat, light, and peroxides and inhibited
by stabilizers, such as the monomethyl ether of hydroquinone or hydroquinone itself. These phenolic inhibitors are effective
only in the presence of oxygen. The highly exothermic, spontaneous polymerization of acrylic acid is extremely violent.

In this section are listed typical examples of reactions other than polymerization, which is discussed in Section Uses. Several
review articles and monographs [1-7] describe the rich chemistry of acrylates and acrylic acid.

Addition Reactions. Acrylic acid and acrylates combine readily with substances, such as hydrogen, hydrogen halides and
hydrogen cyanide, that customarily add to olefins [8]:

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where R = H, alkyl, or aryl, and X = H, halogen, or CN.

Michael additions of organic substances take place in the presence of basic catalysts, such as tertiary amines, quaternary
ammonium salts, and alkali alkoxides:

and R, R = alkyl or aryl.

Ammonia and amines are sufficiently basic to react without a catalyst: where X = NH2 , NHR [9], [10], NRR [11],
heterocycles [12-14], NRCOR, or NHNR2 [15]. The addition of only one molecule of NH3 (for addition of two, see below)
can be achieved with an aqueous solution of ammonia and ammonium carbonate [16].

The addition of aromatic amines or amides and tert-alkyl primary amines is more effectively promoted by acids. Amines may
attack both the vinyl and carboxyl functions, but the products of such reactions decompose to give N-substituted amides.

Alcohols [17], phenols, hydrogen sulfide [14], [18], and thiols [19], [20] also add under basic conditions. Hydrogen sulfide in
the presence of sulfur and ammonium polysulfide or amine catalysts gives polythiodipropionic acids and esters [19], [21]:

where R = H, alkyl, or aryl.

Other examples of HX additions to acrylic acid and acrylates are:

and R = alkyl or aryl [22-24].

Additions of aromatic hydrocarbons are promoted more efficiently by Lewis acids [25].

If further acidic hydrogen atoms are available in the addition product, a second (and third) molecule of acrylic acid or ester
adds. This is the case in the reaction of acrylic acid or ester with H2S, NH3, RNH2, and pyrrole.

Other examples of addition reactions are the following:

where R = H, alkyl, or aryl [3, 26, 27].

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Heterocyclic substances often can be formed by subsequent reaction of the carboxyl function, especially with bifunctional
nucleophiles [23], [28]:

where R = H, alkyl, or aryl.

Substituted ring compounds are formed readily by DielsAlder reactions [30], [31]:

Acrylates also undergo cobalt- or rhodium-catalyzed hydroformylation reactions [32], [33]:

where R = alkyl or aryl.

At elevated temperature or on longer storage acrylic acid dimerizes:

In the presence of catalysts such as tributylphosphine, acrylates can also dimerize to give 2-methyleneglutarates [34]:

where R = alkyl or aryl.

Reactions of the Carboxyl Group. Acrylic acid is converted readily into its corresponding salts, into acrylic anhydride by
reaction with acetic anhydride, or into acryloyl chloride by reaction with benzoyl or thionyl chloride. The esterification of
acrylic acid and transesterification of acrylic esters are economically the most important reactions (see Section Esterification).

Some other examples are:

where R, R = alkyl or aryl [35-37].

1.3. Production
Commercial acrylic acid is mostly produced from propene, which is also the raw material for the production of acrolein. In the
past, acrylic acid and its esters were produced by various processes some of which are summarized here (see [5], [6], [38],
[39]) and are still in use to a small extent.

Processes Based on Acetylene ( Acetylene). The stoichiometric synthesis of acrylic acid and its esters from acetylene
proceeds at atmospheric pressure and at 40 C in the presence of acid and nickel carbonyl:

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where R = H, alkyl, or aryl.

The reaction was discovered by W. REPPE in 1939. Rhm & Haas and Toa Gosei Chemical have used this method as well as
the modified, non-stoichiometric Reppe process, but both have been abandoned because of the difficulties in handling the
toxic and corrosive nickel carbonyl.

High-Pressure Reppe Process. The process employed by BASF and Badische Corp. proceeds at approximately 14 MPa
and 200 C with a nickel bromide copper(II) bromide catalyst:

However, the safety and pollution control problems with nickel carbonyl (formed in the process) and the high cost of
acetylene are disadvantages of this process. It has largely been replaced by the direct oxidation of propene although BASF
still produces part of its acrylic acid by this process.

Acrylonitrile Hydrolysis ( Acrylonitrile). This method is economically unattractive because of the low yield based on
propene and the large quantities of NH4HSO4 waste. The process has been abandoned by Ugine Kuhlmann, Mitsubishi
Petrochemical, and Mitsubishi Rayon. However, it is still on stream at Asahi Chemical.

Ketene Process [6], [40]. Acetic acid or acetone is pyrolyzed to ketene in this process which has long been abandoned by
Celanese and B. F. Goodrich. The many steps and toxicity of -propiolactone are major disadvantages.

R = H or alkyl.

Ethylene Cyanohydrin Process. Ethylene cyanohydrin is generated by addition of hydrogen cyanide to ethylene oxide. The
product then is hydrolyzed to acrylic acid using sulfuric acid. This process was used by Union Carbide and Rhm & Haas, but
has been abandoned because of problems in dealing with HCN and the NH4HSO4 waste.

1.3.1. Propene Oxidation

Propene oxidation involves heterogeneous catalytic oxidation of propene in the vapor phase with air and steam to give acrylic
acid. Generally the product leaving the reactor is absorbed in water, extracted with an appropriate solvent, and then distilled
to give technical grade glacial acrylic acid.

Oxidation Catalysts. Research on catalysts for propene oxidation to acrylic acid began in the latter half of the 1950 s. The
two methods for the heterogeneously catalyzed gas-phase oxidation of propene are single-step and two-step processes:

Single-step process:

Two-step process:

Many patents have been issued in both cases. The yield in the single-step process is at best approximately 50 60 % [38],
[41-43]. Another drawback is limited lifetime of the catalyst, which is a multicomponent system composed of polyvalent
oxides with molybdenum oxide as the main component and tellurium oxide as the promoter. The life of the catalyst is short
because of the tendency of tellurium oxide to sublime.

The two-step reaction (Fig. 2) requires different reaction conditions and different catalysts to produce optimum conversion
and selectivity in each step. Research has focused on this process, in which the oxidation of propene to acrolein and the
oxidation of acrolein to acrylic acid employ separate catalysts. The steps are operated at different temperatures to permit
high overall efficiency.

Figure 2. Schematic diagram of acrylic acid production (oxidation section)

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First-stage catalysts are acrolein-selective propene-oxidation catalysts. The total yield of acrolein and acrylic acid is more
than 85 % ( Acrolein and Methacrolein).

The early second-stage catalysts [43] for acrolein oxidation to acrylic acid were based mainly on cobalt-molybdenum oxides
[44]. They had fairly low activity even at high reaction temperatures and gave yields of less than 70 mol %. Most catalysts are
composed of molybdenum and vanadium oxides. In 1959, Distillers first proposed a molybdenum-vanadium catalyst system
in which the atomic ratio of molybdenum to vanadium was one-to-one [45]. The maximum yield obtained was 30 % at about
400 C. Since then further studies have shown that only a relatively small amount of vanadium is required. In addition, other
elements and carriers have been shown to increase the activity and yield. They have been used for the preparation of multi-
component metal-oxide catalysts that contain one or more of the elements copper, arsenic, uranium, aluminum, tungsten,
silver, manganese, germanium, gold, barium, calcium, strontium, boron, tin, cobalt, iron, or nickel in addition to molybdenum
and vanadium. Supported on an aluminum sponge, the catalyst described in [46] shows good activity and yield. Table 5 lists
patented acrolein oxidation catalysts that have relatively high activities and yields. All of these catalysts are metal oxides.

Table 5. Catalyst for the second step of acrylic acid production

Catalyst composition (support) Reaction Acrolein One-pass yield References

neglecting oxygen temperature, conversion, of acrylic acid,
C % mol %

Mo12V1.9Al1.0Cu2.2 (Al sponge) 300 100 97.5 [46]

Mo12V3W1.2 (SiO2) 240 98.0 87.0 [47]
Mo12V3W1.2Mn3 255 99.0 93.0 [48]
Mo12V2W2Fe3 230 99.0 91.0 [49]
Mo12V3W1.2Cu1Sb6 272 99.0 91.0 [50]
Mo12V4.6Cu2.2W2.4Cr0.6 (Al2O3) 220 100.0 98.0 [51]
Mo12V2(Li2SO4)2 300 99.8 92.4 [52]
Mo12V4.8Cu2.2W2.4Sr0.5 (Al2O3) 255 100.0 97.5 [53]
Mo12V2.4Cu0.24 (SiC) 290 99.5 94.8 [54]
Mo12V3W1.2Ce3 288 100 96.1 [55]
Mo12V4.7W1.1Cu6.3 260 99.0 96.0 [56]

Process Conditions. The conditions in the first step correspond to conditions in the acrolein synthesis (see Acrolein and
Methacrolein Production). The catalysts used in the second step require reaction temperatures from 200 to 300 C and
contact times from 1 to 3 s. They give almost 100 % conversion of acrolein and yields of acrylic acid greater than 90 %.

Acid Recovery and Purification. The effluent gas from the second-stage multi-tube reactor in Figure 2 is cooled to about
200 C and then fed to the absorbing column to be scrubbed with water. Because the effluent gas contains a large amount of
steam, acrylic acid usually is obtained as an aqueous solution of 20 to 70 wt % [57]. Alternatively, the acid may be absorbed
by an organic solvent such as biphenyl, diphenyl ether, or a carboxylic ester with a boiling point higher than 160 C [58].
Then the steam in the reaction gas does not condense in the absorbing column, but is discharged with other gases from the
column top. This method reduces energy consumption in the subsequent purification step, but it also increases the loss of
acrylic acid and solvent from the column top.

After the absorption in water, the acrylic acid is purified by extraction with an organic solvent and then distillation. Various
solvents can be used for the extraction. The first group (light solvents) includes those with boiling points lower than acrylic
acid, such as ethyl acetate, butyl acetate, ethyl acrylate, and 2-butanone, as well as combinations of these [59]. The second
group (heavy solvents) has boiling points higher than acrylic acid (e.g., tert-butyl phosphate, isophorone, and aromatic
hydrocarbons [60]). Mixtures of these light and heavy solvents form a third group [61], [62].

Figure 3 represents the separation and purification process using a light extraction solvent. The aqueous acrylic acid from the
absorbing column is introduced into the extraction column (a) countercurrent to an organic solvent. The solvent must have a
high distribution coefficient for acrylic acid and low solubility in water, and it must form an azeotrope containing a high

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percentage of water. The extract from the top of the extraction column goes to the solvent-separation column (c), where the
solvent and water are distilled overhead and the solvent is separated and recycled to the extraction column.

Figure 3. Schematic diagram of acid recovery and purification section

a) Extraction column; b) Raffinate-stripping column; c) Solvent-separation column; d) Light-ends cut column; e) Product
column; f) Decomposition evaporator

The bottom stream from the extraction column and the water from the overhead of the solvent-separation column are sent to
the raffinate-stripping column (b), where a small amount of solvent is recovered by distillation. The waste water from the
raffinate-stripping column is biologically treated or incinerated.

The bottom fraction from the solvent-separation column is fed to the light-ends cut column (d), where acetic acid is distilled
off and, if desired, recovered. The crude acrylic acid from the bottom of the light-ends cut column is sent to the product
column (e), where acrylic acid of high purity is obtained overhead. The material from the bottom of the product column
containing acrylic acid dimer is fed to the evaporator (f), where the dimer is decomposed to the monomer. The evaporator
residue, composed of acrylic acid oligomers, polymers, and inhibitors, is withdrawn and burned as waste oil.

Because acrylic acid is readily polymerized, distillation columns are operated with an inhibitor, such as hydroquinone or
hydroquinone monomethyl ether, in the presence of oxygen, and at reduced pressure to lower the distillation temperature.
The purity of acrylic acid produced by this process usually exceeds 99.5 wt %, and the purified yield is about 98 %.

In a heavy-solvent extraction process the solvent is not distilled and therefore the energy consumption is less than in a light-
solvent process. However, other problems exist, such as the loss of solvent by decomposition and the inferior quality of the
product. In the processes using mixtures of light and heavy solvents, the purification system is complex. The light-solvent
process is therefore the most suitable for a commercial plant.

Other purification methods also have been reported. In one of these, the acrylic acid is first oligomerized in aqueous solution
in the presence of a catalyst such as sulfuric or phosphoric acid. Next the water is distilled, and finally the residual oligomer is
decomposed at 120 to 200 C to obtain acrylic acid [63]. In another process, the acrylic acid is extracted from the aqueous
solution with butyl acrylate or octanol. It is then directly esterified with an alcohol to form an acrylate without isolation of the
acrylic acid [64], [65]. These processes have not yet been used commercially, probably because of high energy consumption
or problems with the product quality.

1.3.2. Esterification
Although acrylic acid can be esterified in the vapor phase [66], [67], the liquid phase esterification is industrially more
important. Two types of acid catalyst are used: a strong acid, such as sulfuric acid or p-toluenesulfonic acid [68], or a solid
acid, such as a cation-exchange resin [69]. Although sulfuric acid is superior to ion-exchange resins, its use causes problems
in waste disposal. In general, cation-exchange resins are favored for esterification using such alcohols as methanol and
ethanol, whereas sulfuric acid is favored for higher alcohols having slower rates of esterification (e.g., pentanols and
octanols). Liquid phase reaction of acrylic acid with ethylene in the presence of sulfuric acid does not seem economically
feasible for producing ethyl acrylate [70], because of the large quantities of sulfuric acid that are needed.

Lower Alkyl Acrylates (see Fig. 4). Acrylic acid and a small excess (10 30 %) of an alcohol are fed into the fixed-bed
reactor (a) which is packed with a cation-exchange resin and operated at a temperature of 60 to 80 C. The reaction liquid
then goes to the ester stripper (b) where the desired ester, water, and unreacted alcohol are removed overhead using part of
the bottoms from the light-ends column (e) as reflux. The bottom liquid from b contains unreacted acid and is recycled to the
reactor. Part of the recycled liquid is fed into the bottom stripper (c), where high-boiling materials, such as inhibitors,
impurities, and polymers, are removed to prevent their accumulation in the reaction system.

The acid-free mixture of ester and alcohol distilled from the ester stripper (b) is fed into the extraction column (d), where the
alcohol is extracted with water fed from the top of the column. The raffinate from the top of the column goes into the light-
ends cut column (e), where light-ends such as water, acetate, and alcohol are separated overhead.

The extract from the bottom of the extraction column is fed into the alcohol recovery column (f), where the alcohol is
recovered for reuse in the reaction. Part of the bottom liquid is reused as extracting water; the rest is taken out as waste,
concentrated, and either treated biologically or incinerated.

Crude ester from the bottom of the light-ends column is distilled in the product column (g) to obtain acrylate of high purity.
The bottom liquid from the product column is recycled (via the inhibitor tank) to the ester stripper (b) and light-ends cut
column (e) to be reused as an inhibitor. However, a part of it is sent to the bottom stripper (c) to recover ester and separate
high-boiling materials such as polymers.

Polymerization inhibitors, such as hydroquinone or phenothiazine, are added to each column. The light-ends cut column and
the product column are operated at reduced pressure to permit lower distillation temperatures.

Figure 4. Esterification lower alkyl acrylate process

a) Esterification reactor; b) Ester stripper; c) Bottom stripper; d) Extraction column; e) Light-ends cut column; f) Alcohol-

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recovery column; g) Product column

This process for making alkyl acrylates is quite economical because only a small excess of alcohol is applied and the
inhibitor is reused; this leads to low energy and inhibitor consumptions. The yield reaches 95 % and 97 % based on acrylic
acid and on alcohol, respectively. The purity of the product exceeds 99.5 wt %.

Higher Alkyl Acrylates (see Fig. 5). The esterification reaction is preferably carried out batchwise in the presence of an
organic solvent as entrainer and sulfuric acid as catalyst. The water formed is separated through the top of the azeotropic-
distillation column (b). The reaction conditions are: atmospheric pressure, temperature 85 95C, reaction time 3 5 h,
molar ratio (alcohol to acid) 1.0 1.1.

After completion of the esterification, the reaction liquid is cooled to 60C and then transferred to tank (c) where the sulfuric
acid is neutralized with alkali. The oil and water layers are separated and stored in tanks d and e, respectively. The oil layer
is fed into the solvent-recovery column (f) and subsequently into the alcohol-recovery column (g) for distillation. The solvent
and alcohol are recovered overhead and reused in the reaction.

The crude ester obtained from the bottom of the alcohol-recovery column is fed into the product column (h) where purified
acrylic ester is obtained by distillation. The bottom liquid mainly is recycled to the reactor and the alcohol-recovery column to
be reused as supplementary inhibitor. However, part of the liquid is fed into the bottom stripper (i) to recover valuable
materials that are resupplied to the product column. High-boiling waste composed of polymers, inhibitors, and other
impurities is taken out of the bottom stripper and incinerated.

The water from the water-layer tank (e) is fed into the organic stripper (j) together with the water layer from the top and the
bottom of the solvent-recovery column (f). The oil layer obtained from the top of the solvent-recovery column (f) is recycled
into the oil-layer tank. The waste obtained from the bottom of the organic stripper (j) is either treated biologically or
incinerated after concentration.

As in the lower alkyl acrylate process, hydroquinone, its monomethyl ether, or phenothiazine is added to each column, and
the alcohol-recovery and product columns are operated at reduced pressure.

Figure 5. Esterification higher alkyl acrylate process

a) Esterification reactor; b) Azeotropic-distillation column; c) Neutralization tank; d) Oil-layer tank; e) Water-layer tank; f)
Solvent-recovery column; g) Alcohol-recovery column; h) Product column; i) Bottom stripper; j) Organic stripper

The yield reaches 95 % and 96 % based on acrylic acid and on alcohol, respectively. The purity of the product exceeds
99.5 wt %.

1.4. Quality Specifications and Analysis

Production control requires monitoring the propene and oxygen concentrations in the gas phase of the oxidation. These are
checked periodically to maintain optimum reaction conditions and avoid entering the range of flammability. Propene is
determined by GLC with flame ionization detection, oxygen by a magnetic meter [71].

The purity of acrylic acid and its esters depends on the production method employed. Table 6 shows quality standards for
some of these products. The purity of acrylic acid and its esters is commonly determined from the percentage of impurities
measured by GLC with a flame ionization detector. Occasionally the purity of acrylic acid is determined by titration with a
base.

Table 6. Quality specifications of acrylic acid and estersa [6]

Acrylic acid Methyl Ethyl Butyl Octyl

acrylate acrylate acrylate acrylate

99 % 80 %, aq.

Purity b wt %, min 99.0 80.0 99.0 99.0 99.0 99.0

Acid c wt %, max 0.005 0.005 0.005 0.005
Water wt %, max 0.20 0.05 0.05 0.05 0.05
Color APHA, max 20 20 20 20 20 20

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Inhibitor d ppm 200 200 15 5 15 5 15 5 15 5

a Authorized by the Japanese Acrylic Acid and Esters Industrial Association;

b determined by GLC;
c as acrylic acid;
d as hydroquinone monomethyl ether.

In addition to the purity, the polymerization characteristics are important because acrylic acid and acrylates are used chiefly
to make polymers. Polymerization characteristics are determined by examining polymerization patterns such as induction
period and temperature elevation under fixed polymerization conditions (temperature, concentration, catalyst, etc.) The
degree of polymerization of highly purified acrylic acid is greatly decreased in the presence of trace amounts of heavy metals
such as copper, or of aldehydes such as acrolein and furfural.

1.5. Storage and Transportation

Acrylic acid and its esters are usually stabilized with inhibitors such as phenothiazine, hydroquinone, or hydroquinone
monomethyl ether. Because phenolic inhibitors are only effective in the presence of oxygen, the monomers must be stored
under air (usually normal air for acrylic acid and air with reduced oxygen concentration for esters). The safe handling of these
products requires the use of proper protective equipment such as rubber gloves and vapor-proof goggles and masks.

Acrylic Acid. Acrylic acid normally contains 50 to 500 ppm of an inhibitor to prevent polymerization. Because of its relatively
high corrosiveness, it should be stored in equipment made of or lined with glass, polyethylene, polypropylene, or stainless
steel. In addition, it should be kept at 15 to 30 C and away from direct sunlight. Freezing should be avoided because it tends
to localize the inhibitor. If acrylic acid should freeze, however, it should be melted by using a warm water or air bath below
30 C. Agitation of the acrylic acid during the melting is recommended to avoid any localized heating. Acrylic acid often is
used as an 80 % aqueous solution which has a freezing point of 3 to 5 C.

Acrylic Esters. In general, a lower level of inhibitor is required for acrylic esters than for the acid, although the range is still
50 to 500 ppm. The esters are less corrosive than the acid and thus can be stored in equipment made of or lined with carbon
steel or phenolic resin, in addition to glass, polyethylene, and polypropylene. Grades of acrylates containing little or no
inhibitor are available. These products should be carefully stored at temperatures of 0 to 10 C. Methyl and ethyl acrylates
have very low flash points and form explosive gas mixtures in air, even at room temperature. Thus, even though oxygen is an
effective inhibitor, the oxygen concentration in large storage tanks is usually kept at 6 to 8 vol % to prevent the formation of a
flammable mixture.

1.6. Uses
Acrylic Acid. The primary use of acrylic acid is as an intermediate in the production of acrylates. Polymers of the acid and its
sodium salts are used increasingly in flocculants and dispersants with the polymeric sodium salts having more industrial
importance ( Polyacrylamides and Poly(Acrylic Acids)).

Acrylic Esters. Acrylic esters are used exclusively for the production of polymers ( Polyacrylates). The polymers are
used mainly for coatings, paints, adhesives, and binders for leather, paper, and textiles.

About 80 % of the methyl ester produced is used as a copolymer component of acrylic fibers ( ). The ethyl ester is used
for both solvent- and water-based paints, and in textiles as a binder in nonwoven fabrics and flocking. It generally is used in
areas where more rigidity is required than can be obtained with the butyl ester. The butyl ester is growing in use, mainly in
water-based paints and adhesives. The 2-ethylhexyl ester is used for almost the same purposes as the butyl ester, with a
large demand for it in stick-on labels and in the caulking of building materials.

1.7. Some Special Acrylates

Esters with Polyhydric Alcohols. Representative multifunctional acrylates are trimethylolpropane triacrylate, pentaerythritol
tri- or tetraacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and poly(ethylene glycol) diacrylate (n = 2 14).
They usually are produced by direct esterification of acrylic acid with the corresponding polyhydric alcohol in the presence of
an entrainer and an acid catalyst, such as sulfuric acid or p-toluenesulfonic acid. Because these esters have high boiling
points, they cannot be purified by ordinary distillation. Instead, the reaction mixture is neutralized, the entrainer removed, and
the product washed with water [3], [72].

The esters are used as cross-linking agents and modifiers in rubber and synthetic resins, in adhesives, and as active diluents
in photosensitive resins. They are also applied in the coating and ink industries because they can be cured with ultraviolet
light [73], [74] or electron-beam radiation [75]. Proper protection is required when handling these eye and skin irritants.

2-Hydroxyalkyl Acrylates. Two industrially important multifunctional esters are 2-hydroxyethyl acrylate and 2-hydroxypropyl
acrylate. These are produced by liquid-phase esterification of acrylic acid with ethylene oxide or propylene oxide in the
presence of a Lewis acid catalyst, such as a chromium [76] or ruthenium [77] compound, or the iron salt of an organic acid
[78]. Because this reaction readily produces di(alkylene glycol) monoacrylates and alkylene glycol diacrylates as byproducts,
a highly efficient catalyst is required. Although vapor-phase catalytic synthesis using magnesium oxide has been proposed
[79], the liquid-phase esterification is preferred. These esters are used especially as cross-linking agents in heat-cured
paints, adhesives, textile preparations, etc. They are toxic and lacrimatory, cause blistering of the skin, and may give rise to
long-term sensitivity. Inhalation of the vapor causes nose, eye, and throat irritation.

Other Derivatives. Halogenated derivatives such as 2-chloroacrylic acid [80], [81], 2,3-dibromopropyl acrylate [82],
tetrafluoropropyl acrylate, and octafluoropentyl acrylate, have potential uses as fine chemicals. Dialkylaminoethyl acrylates
are produced by transesterifying methyl acrylate with the corresponding amino alcohol.

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1.8. Economic Aspects
Western world production capacities of acrylic acid and its esters as of late 1982 were 839500 t/a and 1277500 t/a,
respectively (Table 7). Plants based on other processes, such as the ketene and cyanohydrin methods (see Section
Production), were shut down during the past decade because of inefficiency.

Table 7. Estimated regional production capacities for acrylic acid and its esters in the western world (t/a)

Acid Esters

1982 1994* 1982 1993*

United States 430 000 690 000 700 500 587 000
Western Europe 282 000 640 000 380 000 312 000
Japan 117 500 420 000 182 000 206 000
Others 10 000 15 000

Total 839 500 ca. 2 000 000 1 277 500 ca. 1 200 00

* [118]

In fact it appears that the propene oxidation route will continue to be the most economical process for quite some time.
Announced additional capacities of 280000 and 380000 t/a for the acid and esters, respectively, will all be based on propene
oxidation.

Consumption of acrylic acid for uses other than as an intermediate in ester production ranges from 5 to 9 % of the total,
although demand for and consumption of both acid and esters varies from region to region. Table 8 gives estimated end-use
percentages in three regions. Surface coatings provide the largest market for the esters in all three regions.

Table 8. Estimated distribution of end uses of acrylic esters (% of total)

United States Western Europe Japan

Surface coatings 42 35 34
Textiles 23 18 16
Acrylic fibers 6 7 14
Adhesives 5 15 20
Others 24 25 16

1.9. Toxicology and Occupational Health

Acrylic Acid. Acrylic acid is moderately toxic and very corrosive [84]. Ingestion may cause severe gastrointestinal burns.
The vapor is an irritant to the eyes and respiratory tract and skin contact may cause burns. Physiological response data are:

LD50 340 mg/kg (rat, oral)

LC50 3600 mg/m3 (rat, inhalation, 5 L, 4 h)
LD50 280 mg/kg (rabbit, skin)

The TLV on a time weighted average (TWA) is 10 ppm or 30 mg/m3.

Acrylic Esters. Acrylic esters are of moderately acute toxicity, which decreases with an increase in the number of carbon
atoms in the alkyl group (Table 9). Liquid methyl and ethyl acrylates severely irritate the skin and mucous membranes and
are corrosive to the eyes, whereas the butyl and 2-ethylhexyl acrylates have less severe effects. Methyl and ethyl acrylate
vapors are very lacrimatory, extremely irritating to the respiratory tract, and are corrosive to the eyes, causing corneal injury.
The lacrimatory effect of the butyl and 2-ethylhexyl esters is weak, but their vapors may cause dizziness, headache, nausea,
and vomiting.

Table 9. Physiological response data and exposure levels of some acrylates

Methyl Ethyl acrylate Butyl acrylate 2-Ethylhexyl

acrylate acrylate

LD50 (rat, oral), mg/kg 300 1020 3730 5660

LCLo (rat, inhalation, 4 h), 3500 4000 5500

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mg/m3
LD50 (rabbit, dermal), 1243 1950 2000 8480
mg/kg
TLV (TWA) 10 ppm, 5 ppm, 10 ppm,
35 mg/m3 20 mg/m3 55 mg/m3
MAK 10 ppm, 25 ppm,
35 mg/m3 100 mg/m3

Methyl and ethyl acrylates can be absorbed through the skin in toxic amounts, and overexposure to the vapor can result in
fatal pulmonary edema. However, their noticeable odors and irritating effects reduce the likelihood of significant exposure.

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2. Cyanoacrylates
Klaus Marten

The monofunctional 2-cyanoacrylates, CH2 = C(CN)-COOR, have been known for many years. Technical developments,
based on the original patents of 1949 [85], led in 1954 to the first viable production process [86], [87]. Since then these
compounds have achieved a considerable growth rate on the market. The 2-cyanoacrylates are utilized almost exclusively as
adhesives. The methyl, ethyl, butyl, allyl, and methoxyethyl esters are available with different setting characteristics and
rheological properties, depending on the requirements of the application.

Physical Properties. Pure 2-cyanoacrylates are clear, colorless liquids at room temperature and have a characteristic odor.
Their physical properties are listed in Table 10.

Table 10. Physical properties of industrially important 2-cyanoacrylates

Property Methyl Ethyl Butyl Allyl Methoxyethyl

CAS registry number [137-05-3] [7085-85-0] [6606-65-1] [7324-02-9] [27816-23-5]

Molecular formula C5H5NO2 C6H7NO2 C8H11NO2 C7H7NO2 C7H9NO3
Mr 111.10 125.13 153.18 137.14 155.15
bp, C/p, kPa 48 54 53 115/2.53 80 82/0.13
49/0.33 56/0.34 56/0.27
0.36 0.40 0.33
Viscosity, mPa s 2.20 1.86 2.08 6.4
Heat of polymerization in
isobutyronitrile at 25 C,
kJ/mol 57.7 58.2 67.8
Refractive index, 1.4406 1.4349 1.4291 1.4426
(20 C)
Density at 20 C, g/cm3 1.1044 1.0501 1.0009 1.0578
Vapor pressure at 25 C, <0.27 <0.27 <0.27
kPa

Chemical Properties. The vinyl structure of the 2-cyanoacrylates makes them liable to spontaneous polymerization. This is
desirable for their use as reactive adhesives, but causes significant difficulties in synthesizing and especially in purifying
them.

Because the chain propagation reaction can be initiated by either an ionic or a radical mechanism, the rate of polymerization
depends on temperature, humidity, light, and the presence of polymerization accelerators, such as peroxides and bases. The
2-cyanoacrylates are, however, adequately stable if stored under cool conditions in the presence of suitable inhibitors. In
addition to polymerization, they undergo the other reactions typical of vinyl compounds (e.g., addition).

Production. Many different processes can be used to manufacture 2-cyanoacrylates. The important step in most of the
published syntheses is the classical Knoevenagel reaction using formaldehyde and a cyanoacetic ester. In this first step
oligomeric cyanoacrylates, water, and other byproducts are formed. The reaction can be catalyzed by bases (e.g., amines)
[86], [87], alkali metal tetraborates, metal carbonyls [89], or phase-transfer catalysts [90]. The raw condensation product from

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the first reaction is depolymerized thermally (either continuously or discontinuously) [91] and purified by distillation,
chromatography on alumina or silica gel [92], crystallization in polyethylene columns [93], or treatment with zinc chloride [94].

Alternatively, 2-cyanoacrylates can be manufactured by the ethoxycarbonylation of cyanoacetylene in the presence of nickel
carbonyl [95].

Uses. 2-Cyanoacrylate-based formulations have been a valuable component of modern adhesive technology for many years.
Their ability to join the most dissimilar materials quickly, firmly, and durably has insured a wide field of applications. They are
used in the electrical and electronics industries as well as many areas of mechanical engineering, such as automobile, ship,
and aircraft construction. In addition to these purely technical applications, the 2-cyanoacrylates are used in medicine to
close wounds.

Special properties to meet specific requirements are obtained by the use of additives or a manufacturer's proprietary process.
Such parameters as hardening time [96-98], viscosity [99], [100], relative strength [101], resistance to hydrolysis [102], [103],
heat resistance [104], [105], flexibility of the mature adhesive [106], [107], and shelf life [108-110] commonly are varied (
Adhesives).

Toxicology and Occupational Health. Both the MAK and the TLV exposure limits for 2-cyanoacrylates have been set at
2 ppm. Adequate ventilation of the work place is therefore necessary if these substances are in continual use. Further
information can be obtained from the relevant documentation provided by suppliers. Although many years of practical use
have not yet led to any significant damage to health, the toxicology of 2-cyanoacrylates requires further investigation [111],
[112]

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3. Acrylamide
Helmut Greim

Properties. Acrylamide [79-06-1], 2-propenamide, CH2 = CHCONH2, Mr 71.08, mp 84.5 C, usually forms white crystalline
platelets. It is very toxic.

Acrylamide is most conveniently handled as an aqueous solution because the dry powder forms a fine, toxic dust. It is
soluble in water, alcohols, and acetone but insoluble in benzene and heptane.

Acrylamide and polyacrylamide can be converted into various products by the usual addition reactions of the double bond
and especially by reactions of the amide group:

N-Alkyl derivatives of acrylamide are prepared by the reaction of acryloyl chloride with the corresponding amine, by the
dehydrochlorination of 2-chloropropionamide, or by the amination of acrylic acid or esters [113].

Production. Acrylamide was first produced on a large scale, by American Cyanamid, in 1954. It is currently produced from
acrylonitrile either by homogeneous sulfuric acid hydration or by heterogeneous catalytic hydration.

Sulfuric Acid Process. One mole of Acrylonitrile ( Acrylonitrile) is added to a solution of 1 mol sulfuric acid and 1 mol of
water at 60 C. The mixture is slowly heated to 80 C, kept for an hour at this temperature, and then cooled to 40 C.
Ammonium sulfate precipitates on neutralization with ammonia and is filtered out. The acrylamide, which crystallizes on
cooling the mother liquor to below 10 C, is purified by recrystallization from benzene.

Catalytic Hydration Process. Figure 6 shows a flow diagram of this process. A 50 wt % solution of acrylonitrile in water is
slurried with a catalyst such as Raney copper and kept at 120 C for 2.5 h. Conversion of acrylonitrile is greater than 50 %
and selectivity to the amide is nearly 100 %. This process conveniently makes an aqueous solution of 30 to 50 wt %
acrylamide because of the large amount of water required in the reaction.

Figure 6. Catalytic hydration of acrylonitrile

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Biological Process. A patented biocatalyst enables the hydration of acrylonitrile at room temperature and pressure in a
process developed by Nitto Chemical Industry Co. (Tokyo). The catalyst is an enzyme derived from one of several bacterial
genera [114].

Uses. Acrylamide is made mainly into water-soluble polymers and copolymers used in flocculants, papermaking aids,
thickening agents, surface coatings, and enhanced oil recovery [113], [115] ( Polyacrylamides and Poly(Acrylic Acids)).

Toxicology and Occupational Health. The health consequences of human exposure to acrylamide have been repeatedly
evaluated [118-122]. Most of the information given in the following is derived from these reports in addition to more recent
scientific publications.

Effects Assessment. In humans and laboratory animals, single or repeated exposures to acrylamide caused local irritations
on contact with the skin and neurological symptoms. The peripheral neuropathy is a result of long-term accumulation and
appears after a latent period. Its onset parallels the accumulation of acrylamide bound to proteins in the nervous system and
to hemoglobin. In a two year's study in rats exposed to acrylamide via drinking water the lowest observed effect level (LOEL)
for peripheral neuropathy was 0.5 mg/kg.

Acrylamide is readily absorbed during oral, inhalation and dermal exposure. In rats the major route of metabolism is direct
conjugation with glutathione and subsequent urinary excretion of the conjugate. The compound is also metabolized by
cytochrome P-450 2E1 dependent monooxygenase activity forming the epoxide glycidamide [123].

Both, acrylamide and glycidamide interact with proteins and form hemoglobin adducts. Glycidamide interacts with DNA and is
considered the genotoxic and carcinogenic intermediate. Mice form more glycidamide than rats and there is an indication that
humans form less glycidamide than rats. These species differences in metabolism explain the lower potency to induce
tumors in rats than in mice and suggest that humans are less sensitive than rats.

In rats acrylamide induced increased incidences of thyroid adenomas, testicular mesotheliomas, adrenal
phaeochromocytomas, fibroadenomas in the mammary gland, and focal hyperplasia in the oral cavity. An increased
incidence of astrocytomas was also detected. The lowest effective dose in these studies was 12 mg/kg bw/da. (mg per
kilogram body weight and day).

In mice skin painting experiments acrylamide initiates the formation of skin tumors. Epidemiological studies have not
revealed tumors in humans. Since the carcinogenic potency of acrylamide in animals is weak the epidemiological studies
may not be sensitive enough to show an increased tumor incidence in man.

Acrylamide is considered to be genotoxic although contradictory results have been obtained in the various assays. In
bacterial systems glycidamide but not acrylamide induced mutations. In mammalian cells in vitro chromosomal aberrations,
micronuclei, sister chromatid exchanges, polyploidy and other cytogenetic effects have been observed. In vivo the compound
was positive in the bone marrow chromosome aberration test and in the micronucleus assay.

Overall, the long term animal studies, its genotoxicity, and the formation of the genotoxic metabolite glycidamide in humans
indicate that acrylamide has the potential to cause cancer in humans. Accordingly, IARC, the EU, and several national
committees classified acrylamide as probably carcinogenic to humans.

In reproductive toxicity studies with rats, the no observed adverse effect level (NOAEL) for reduced fertility was 5 mg/kg
bw/da and for premature embryonic death 2 mg/kg bw/da.

Exposure. The concern in 2002 is the relatively high exposure of consumers from fried, oven-baked, and deep-fried potato
and cereal foods. The Scientific Committee on Food of the European Commission [124] estimates an average daily human
intake of about 1 g/kg considering that differently contaminated food, some of which containing up to 3000 g acrylamide
per kilogram, is consumed. Contamination of certain food had been first detected by the Swedish National Food Agency.
They found that especially potato products such as chips and crisps, but also basic staple foods such as bread and crisp
bread contained varying high levels of acrylamide. Acrylamide was not detected in boiled foods. These results have been
confirmed by analyses of foods in other European countries.

The available information suggests that acrylamide is primarily formed in carbohydrate-rich foods at high temperatures. It is
presently being evaluated whether changes in food processing and cooking may decrease formation of acrylamide.

At the workplace exposure occurs during acrylamide and polyacrylamide production, during grouting and during preparation
of polyacrylamide gels. Low levels have been detected in the drinking water from the use of polyacrylamide flocculants in
water treatment and from the use of polyacrylamides in cosmetics and toiletries [122].

Risk Characterization. The available information indicates that there are concerns regarding neurotoxicity (NOEL 0.5 mg/kg
bw/da), impact on the reproduction system (NOEL 2 mg/kg bw/da) and carcinogenicity. Based on the average daily intake by

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humans via food of 1 g/kg bw/da the margin of safety (MOS) between this exposure and the NOEL of neurotoxicity is 500.

Due to its genotoxic potential no dose threshold for the carcinogenic effect of acrylamide can be established. Using a linear
extrapolation from the carcinogenicity studies in animals the lifetime cancer risk related to a daily intake for 70 years of 1
g/kg acrylamide is about 1 103 (one case of cancer per 1000 individuals).

The TLV-TWA is 0.03 mg/m3 with a skin notation without a STEL, A3: confirmed animal carcinogen. The TRK (Technische
Richtkonzentration) is 0.06 mg/m3. Classification of acrylamide by IARC: probable carcinogen for humans (2b), MAK:
Considered to be carcinogenic to man (Cat. 2).

[Top of Page]

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