Alcohols, Polyhydric 1

Alcohols, Polyhydric
→ Ethylene Glycol, → Propanediols, → Butanediols, Butenediol, and Butynediol, → Glycerol, and → Sugar
Alcohols are separate keywords.

Peter Werle, Degussa AG, Hanau-Wolfgang, Federal Republic of Germany (Section 2.9, Chaps. 3, 4, 5, 6)

Marcus Morawietz, Degussa AG, Hanau-Wolfgang, Federal Republic of Germany (Chap. 2, Sections
2.1 – 2.8)

1. General Aspects . . . . . . . . . . . . . 1 2.6. 2,2-Bis(4-hydroxycyclohexyl)pro-

2. Diols . . . . . . . . . . . . . . . . . . . . . 4 pane . . . . . . . . . . . . . . . . . . . . . 9
2.1. 1,5-Pentanediol . . . . . . . . . . . . . 4 2.7. 1,4-Bis(hydroxymethyl)cyclohexane 9
2.2. 1,3-Propanediols . . . . . . . . . . . . . 4 2.8. 2,2,4-Trimethyl-1,3-pentanediol . . 11
2.2.1. 2,2-Dimethyl-1,3-propanediol 2.9. Vicinal Diols by Hydroxylation of
(Neopentyl Glycol) . . . . . . . . . . . . 4 Olefins with Peracids . . . . . . . . . . 11
2.2.2. Hydroxypivalic Acid Neopentyl 2.9.1. 1,2-Pentanediol . . . . . . . . . . . . . . 11
Glycol Ester . . . . . . . . . . . . . . . . 6 2.9.2. Other 1,2-Diols . . . . . . . . . . . . . . 11
2.2.3. 2-Methyl-2-propyl-1,3-propanediol 3. Triols . . . . . . . . . . . . . . . . . . . . 12
and 2-Butyl-2-ethyl-1,3-propanediol . 7 3.1. Trimethylolpropane . . . . . . . . . . 12
2.2.4. 2-sec-Butyl-2-methyl-1,3-propane- 3.2. Trimethylolethane . . . . . . . . . . . 12
diol . . . . . . . . . . . . . . . . . . . . . 7 4. Tetrols . . . . . . . . . . . . . . . . . . . 13
2.2.5. 1,3-Propanediol . . . . . . . . . . . . . . 7 4.1. Ditrimethylolpropane . . . . . . . . . 13
2.2.6. 2-Methyl-1,3-propanediol . . . . . . . 7 4.2. Pentaerythritol . . . . . . . . . . . . . . 13
2.3. 1,6-Hexanediol . . . . . . . . . . . . . . 8 5. Higher Polyols . . . . . . . . . . . . . . 15
2.4. Hexynediols . . . . . . . . . . . . . . . . 8 5.1. Dipentaerythritol . . . . . . . . . . . . 15
2.4.1. 3-Hexyne-2,5-diol . . . . . . . . . . . . 8 5.2. Tripentaerythritol . . . . . . . . . . . . 15
2.4.2. 2,5-Dimethyl-3-hexyne-2,5-diol . . . 9 6. Toxicology . . . . . . . . . . . . . . . . . 15
2.5. 1,10-Decanediol . . . . . . . . . . . . . 9 7. References . . . . . . . . . . . . . . . . . 16

1. General Aspects with acids and acid anhydrides to form esters,

and with aldehydes or ketones to form acetals or
The properties common to all polyhydric alco- ketals.
hols are determined by the hydroxyl groups: hy- Polyhydric alcohols, especially triols and
drogen bonding leads to high boiling points, high tetrols, are normally regarded as polyols, but
viscosity, and solvency for polar substances. in the literature poly(ether alcohol)s such as
Other important characteristics are the structure poly(ethylene glycol)s and/or poly(ester alco-
of the alcohols and the accessibility of the hy- hol)s are sometimes also classified as polyols.
droxyl groups (primary, secondary, or tertiary),
which influence the chemical behavior and the Production. Each class of polyhydric alco-
thermal stability of the hydroxyl functions. Al- hol has its own basic production method and raw
cohol groups next to a neo structure (e.g., pen- materials. The most important synthetic strate-
taerythritol or neopentyl glycol) exhibit higher gies are presented in Scheme 1.
resistance towards elimination and degradation The reactions can be classified into the fol-
because of the lack of β-hydrogen atoms. Some lowing general categories:
of the important physical properties of the alco-
hols discussed in this article are given in Table 1. a) Epoxidation of alkenes followed by acid-
Important reactions of polyhydric alcohols catalyzed cleavage of the epoxide ring to ob-
are those with isocyanates to form urethanes, tain the 1,2-diol.

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

10.1002/14356007.a01 305
2 Alcohols, Polyhydric
Table 1. Physical properties of polyhydric alcohols

Compound Mr
, bp, mp, Dynamic Flash

Molecular g/cm3 (◦ C) ◦
C (kPa) ◦
C viscosity, point,
◦
formula mPa · s C
(◦ C)

1,5-Pentanediol 104.15 0.992 (20) 240 – 244 (101.3) ca. – 16 128 (20) 136 a
C5 H12 O2 48 (40)
2,2-Dimethyl-1,3-propanediol 104.15 1.060 (20) 209 – 210 (101.3) 130 174 (25) 103 b
(Neopentyl glycol) C5 H12 O2 151.6 c
Hydroxypivalic acid neopentyl 204.26 1.019 (20) 292 (decomp., 50 – 51 70 (60) 161
glycol ester C10 H20 O4 1.000 (85) 103.3)
163 (1)
2-Methyl-2-propyl-1,3- 132.20 0.913 (60) 230 (102.3) 56 – 58 130
propanediol C7 H16 O2 111 – 113 (0.5)
2-Butyl-2-ethyl-1,3-propane- 160.20 0.9266 (50) 132 – 133 (0.7) 40 – 43 8.5 (100) 144
diol
C9 H20 O2
2-sec-Butyl-2-methyl-1,3- 146.22 92 – 97 (0.1) 52.5 (decomp.)
propanediol C8 H18 O2
2-Methyl-1,3-propanediol 90.12 213 (101.3) − 91 68 (25) > 230
C4 H10 O2
1,6-Hexanediol 118.18 0.965 (50) 252 (101.3) 40 – 42 46.86 (48.6) 147 a
C6 H14 O2 0.927 (104) 6.901 (104)
3-Hexyne-2,5-diol 114.15 1.023 (13) ca. 100 (0.1) 40 – 70 6 (90)
C6 H10 O2 113 – 114 (2)
2,5-Dimethyl-3-hexyne-2,5-diol 142.20 96 – 97
C8 H14 O2
1,10-Decanediol 174.29 0.89 (80) 160 (0.65) 71 – 73 15.8 (80) 152 a
C10 H22 O2
2,2-Bis(4-hydroxycyclohexyl)- 240.37 0.958 (155) 235 – 245 (2.7) 125 – 163 114 (152) 152 a
d
propane C15 H28 O2
1,4-Bis(hydroxymethyl)cyclo- 144.24 1.041 (20) 286 (100) 31.5 e 218 (70) 162
hexane C8 H16 O2 0.994 (100) 163.9 (1.33) 40.2 (100)
2,2,4-Trimethyl-1,3-pentanediol 146.23 0.897 215 – 235 46 – 55 27 (50) 110 f
C8 H18 O2 (101.3)
1,2-Pentanediol 104.15 0.980 (20) 210 (101.3) 105
C5 H12 O2
2,3-Dimethyl-2,3-butanediol 118.18 0.967 (20) 174 (101.3) 42 75
(Pinacol) C6 H14 O2
C4 H10 O3
Trimethylolpropane 134.18 1.084 (20) 285 (101.3) 58
C6 H14 O2
Trimethylolethane 120.15 1.210 (20) 283 (101.3) 202
C5 H12 O2
Ditrimethylolpropane 250.34 112 – 114
C12 H26 O5
Pentaerythritol 136.15 1.396 (20) 276 (4) 260 – 262 240 a
C5 H12 O4
Dipentaerythritol 254.28 1.365 (20) 222
C10 H22 O7
Tripentaerythritol 372.42 1.300 (20) 248
C15 H32 O10
a
Pensky-Marten (closed cup).
b
BASF.
c
Eastman.
d
Isomer distribution: cis/cis 3 – 3.5 %; cis/trans 30 – 35 %; trans/trans 60 – 65 %.
e
Softening point.
f
Cleveland (open cup).
 Alcohols, Polyhydric 3

Scheme 1. Synthetic routes to polyhydric alcohols

4 Alcohols, Polyhydric

b) Base-catalyzed aldol addition of formalde- 2. Diols

hyde to the appropriate higher aldehyde, fol-
lowed by reduction, either by Cannizzaro re- 2.1. 1,5-Pentanediol
action with excess formaldehyde and base or
by catalytic hydrogenation. Reduction by the 1,5-Pentanediol [111-29-5], pentamethylene
Cannizzaro reaction causes the formation of glycol, HOCH2 (CH2 )3 CH2 OH, is a colorless
large amounts of formate salt, so that sev- liquid (see Table 1), soluble in water, alcohol,
eral recrystallization steps are required for acetone, and relatively insoluble in aliphatic and
the separation of the salts from the products. aromatic hydrocarbons.
For the catalytic hydrogenation to be worth-
while, the equilibrium of the aldol addition Production. 1,5-Pentanediol usually is pro-
must lie sufficiently to the right, that is, suf- duced by catalytic hydrogenation of glutaric acid
ficient β-hydroxyaldehyde must be formed or of its esters, although dicarboxylic acid mix-
in the first step. tures containing glutaric acid also may be used
c) Addition of water to α,β-unsaturated alde- (see Section 2.3). The crude products are puri-
hydes also results in formation of β-hy- fied by distillation. Manufacturers of 1,5-pen-
droxyaldehydes. The corresponding 1,3-diol tanediol are BASF and Ube Ind.; the world ca-
can be obtained by subsequent hydrogena- pacity is about 500 t/a.
tion.
d) Hydroformylation of epoxides represents Uses. 1,5-Pentanediol is the starting material
the third method for producing β-hy- for the production of various heterocyclic com-
droxyaldehydes for hydrogenation to 1,3- pounds, such as 1-methylpiperidine, which are
diols. In contrast to the aldol method (b), the used in the synthesis of pharmaceuticals and pes-
methods based on Michael addition of wa- ticides. The substance is also used in the pro-
ter (c) and the cleavage of epoxides (a) are duction of fragrances and as a component of
limited to the generation of one 1,3-diol unit. polyesters and polyurethanes.
e) Addition of aldehydes or ketones to acety-
lene to give the alkynediols or the corre-
sponding 1,4-diols by subsequent hydro-
2.2. 1,3-Propanediols
genation.
f) Catalytic hydrogenation of carboxylic acids
2.2.1. 2,2-Dimethyl-1,3-propanediol
and their esters.
(Neopentyl Glycol)
g) Hydrogenation of phenols or phenol deriva-
tives (e.g., bisphenol A).
Neopentyl glycol [126-30-7] has become an in-
dustrially important and versatile diol [1], par-
Uses. The chief use of polyhydric alcohols ticularly as a building block for polyesters and
is as components of saturated and unsaturated polyurethanes.
polyester resins and alkyd resins. These resins,
which are known for their excellent stability, are HOCH2 C(CH3 )2 CH2 OH
used in a wide range of varnishes and coatings.
The addition of polyisocyanates to polyether- This is because of the wide availability of
polyols and polyesterpolyols derived from poly- the starting materials, isobutyraldehyde and
hydric alcohols leads to polyurethanes, which formaldehyde, and the extraordinary stability
are used for the production of elastomers and of its derivatives resulting from the quaternary
various types of foams. Other uses are as syn- structure and the absence of hydrogen atoms in
thetic lubricants, plasticizers, dispersants, fibers, the β-position.
and as additives to poly(vinyl chloride). Some of
the diols are used in the production of pharma- Physical Properties. Neopentyl glycol (see
ceuticals and fragrances. Table 1), colorless crystals, has a phase tran-
sition at 40 – 42 ◦ C. It is hygroscopic at
 Alcohols, Polyhydric 5

relative humidities greater than 50 % and sub- quirements of the hydrogenation and purifica-
limes readily, even somewhat below the melt- tion stages.
ing point. Neopentyl glycol is soluble in wa- If inorganic bases such as potassium car-
ter, alcohols, and ketones, moderately soluble bonate [4] or sodium hydroxide [5], [6] are
in hot aromatic solvents, such as benzene and used as catalysts, satisfactory yields (ca. 80 %)
toluene, and relatively insoluble in aliphatic and of neopentyl glycol can be obtained only with
cycloaliphatic solvents. an excess of isobutyraldehyde. Side products
formed by aldol addition, Cannizzaro reactions,
Chemical Properties. Pure neopentyl gly- or Tishchenko reactions are 2,2,4-trimethyl-1,3-
col is thermally stable up to the boiling point. pentanediol, neopentyl glycol isobutyrate, and
However, in the presence of alkali salts or bases, hydroxypivalic acid neopentyl glycol ester (Sec-
neopentyl glycol decomposes above 140 ◦ C. tion 2.2.2). Salts are also formed which interfere
In addition to the reactions typical of primary with the hydrogenation catalyst or cause decom-
alcohols, such as ester, ether, and carbamate position during distillation. Sodium hydroxide
formation, 1,3-diols give six-membered cyclic always gives some Cannizzaro reaction, which
derivatives with carbonyl compounds, carbon- can be partially suppressed by excess isobu-
ates, phosphites, sulfites, and borates. tyraldehyde and/or water soluble solvents such
as aliphatic alcohols [6].
Production. The aldol addition of isobu- Hydroxypivaldehyde is separated from salts
tyraldehyde (2-methylpropanal) and formalde- by extraction with dibutylether and hydro-
hyde gives hydroxypivaldehyde (3-hydroxy- genated on copper chromite catalyst between
2,2-dimethylpropanal) [597-31-9], which is 175 and 220 ◦ C.
then reduced to neopentyl glycol: In a variant of this process [7] hydrogena-
tion and hydrogenolysis are performed step-
wise at different temperatures (120 – 160 ◦ C and
175 – 190 ◦ C). At the higher temperature, ester
byproducts also are hydrogenated to the corre-
sponding alcohols.
Ruhrchemie [8] has avoided the interference
of alkali salts, formed during the aldol addi-
tion, in the hydrogenation and in the purifica-
Both aldol addition and subsequent reduc- tion stages by diluting the hydroxypivaldehyde
tion are exothermic. Hydroxypivaldehyde can with isobutanol, evaporating the mixture, and
be reduced either by a crossed Cannizzaro reac- then hydrogenating the hydroxypivaldehyde in
tion with equimolar amounts of formaldehyde the gas phase at 110 – 150 ◦ C over cobalt, cop-
and a base, or by catalytic hydrogenation (see per, or nickel catalysts.
Scheme 1). Tertiary amines are the state-of-the-art cata-
Production by the Cannizzaro Reaction. In lysts for the aldol addition.[9]. Hydroxypivalde-
this process, aldol addition and reduction can be hyde is formed rapidly by the reaction of isobu-
performed either simultaneously [2] or in two tyraldehyde (up to 10 % excess), formaldehyde,
stages [3]. However, the individual reactions can and trialkylamine. The reaction is characterized
be controlled more selectively in the two-stage by the complete conversion of formaldehyde,
process. Reduction of hydroxypivaldehyde with which is the main difference to the classical pro-
formaldehyde/sodium hydroxide solution leads cesses for trimethylolpropane and pentaerythri-
to the coproduction of 0.8 – 0.9 t sodium formate tol. The excess of isobutyraldehyde is distilled
per tonne of neopentyl glycol and to high pro- and recycled together with the amine. The reac-
duction costs. The sodium formate has a limited tion runs very selectively and therefore most of
commercial value. the side products which are typical of the pro-
Production by Catalytic Hydrogenation. duction based on the Cannizzaro reaction are
This process usually is performed in two stages. negligible. The conditions of the hydrogenation
The type of catalysts used for the aldol addi- reaction vary from 80 to 200 ◦ C and 35 – 300 bar.
tion has a significant effect on the technical re- Heterogeneous catalysts based on cobalt, cop-
6 Alcohols, Polyhydric

per, or nickel can be used in the fixed-bed re- 2.2.2. Hydroxypivalic Acid Neopentyl
actor [10]. After fractional distillation a very Glycol Ester [11]
good yield of high-purity neopentyl glycol is ob-
tained. Hydroxypivalic acid neopentyl glycol ester, (3-
hydroxy-2,2-dimethylpropyl)-3-hydroxy-2,2-
Quality, Storage, and Transportation. dimethylpropionate (HPN) [1115-20-4] is the
Commercial neopentyl glycol has a purity of monohydroxypivalate of neopentyl glycol:
about 99 % (determination by GLC). Impu-
rities may include neopentyl glycol monofor-
mate, neofpentyl glycol monoisobutyrate, 2,2,4-
trimethyl-1,3-pentanediol, and the cyclic acetal
from the reaction of hydroxypivaldehyde and
neopentyl glycol. The compound has properties similar to
During storage, higher temperatures and neopentyl glycol but in addition specific char-
stacking pressures can lead to caking of the acteristics that are responsible for its increas-
lower stack layers. As a hygroscopic material, ing use. Manufacturers are Eastman Chemi-
neopentyl glycol must be stored dry. cal, BASF, Mitsubishi Gas, and Union Carbide.
World capacity is estimated at 2000 – 2500 t/a.
Producers. Manufacturers are: BASF,
Hoechst Celanese, Degussa-Hüls, Eastman Ko- Physical Properties. Hydroxypivalic acid
dak, Koei, Mitsubishi Gas Chemical, Perstorp, neopentyl glycol ester is a colorless crystalline
and Polioli. World capacity is estimated at about solid with a melting point of 50 ◦ C (see Table 1).
220 000 t/a. It is highly soluble in polar organic solvents; its
solubility in water is limited to 27.4 % at 25 ◦ C;
Uses. The main use of neopentyl glycol is in conversely, 52.4 % water dissolves in HPN.
saturated polyester resins for coil coatings and
internal coating of tins, packing material var- Chemical Properties. Pure HPN can be dis-
nishes, car varnishes, electrical insulation, and tilled at reduced pressure without decomposi-
wire coatings, as well as in alkyd resins for paint tion up to about 200 ◦ C. In the presence of alkali
varnishes, household varnishes, and self-drying metal salt impurities, significant decomposition
industrial and ship varnishes. The alkyd resins occurs even at temperatures of about 150 ◦ C.
can be used as solvent-containing, radiation- Both hydroxyl groups undergo the usual reac-
cured, water-dilutable, and powder varnishes tions of primary alcohols. As with neopentyl
and as high-solids paints. Neopentyl glycol is glycol, the quaternary structure contributes to
gaining importance particularly as a diol com- the excellent stability of HPN derivatives.
ponent in powder coating systems. In addition to
the technological advantages of these varnishes, Production. Hydroxypivalic acid neopentyl
they are highly stable with respect to hydroly- glycol ester is produced by a Tishchenko reac-
sis, to attack by alkali, and to heat; they also are tion directly from hydroxypivaldehyde in the
weather-resistant. presence of a basic catalyst (e.g., aluminum
Neopentyl glycol imparts the same advan- oxide) [12] or classically by thermal treatment
tages to unsaturated polyester resins, which are [13] (Section 2.2.1). Alternatively, it can be syn-
used for gel coats, corrosion resistant contain- thesized by esterification of neopentyl glycol
ers, and in molding materials for building com- with hydroxypivalic acid [14]. High-purity hy-
ponents, etc. In addition, neopentyl glycol is a droxypivalic acid neopentyl glycol ester is ob-
component of polyesterpolyols in plasticizers, tained by subsequent distillation [15].
its esters are synthetic lubricants, it is used as
dispersant for titanium dioxide, and as starting Uses. Hydroxypivalic acid neopentyl glycol
material for polyurethanes. ester is a diol modification agent in polyesters,
polyurethanes, and plasticizers. As a component
of polyester varnish systems, HPN has special
 Alcohols, Polyhydric 7

advantages with respect to flow properties, ad- 2.2.5. 1,3-Propanediol

hesion firmness, flexibility, thermal stability, re-
sistance to light (UV), and impact strength at 1,3-Propanediol [504-63-2] is a colorless liquid
low temperature. The ester is used as a diol at room temperature in contrast to 2,2-dialkyl-
component of powder varnishes, coil coatings 1,3-diols (see Table 1). 1,3-Propanediol is pro-
(e.g., internal coating of cans), electrophoresis duced commercially by Degussa starting from
varnishes, and unsaturated polyester resins; it acrolein [107-02-8].
is used also in radiation-cured varnish resins,
binders for water lacquers, plasticizers, and CH2 CHCHO + H2 O −→ HOHCH2 CH2 CHO
polyurethane foams.
HOHCH2 CH2 CHO + H2 −→ HOHCH2 CH2 CH2 OH

2.2.3. 2-Methyl-2-propyl-1,3-propanediol The addition of water under mild acidic

and 2-Butyl-2-ethyl-1,3-propanediol conditions gives 3-hydroxypropionaldehyde
[2134-29-4] with high selectivity (see
2-Methyl-2-propyl-1,3-propanediol [78-26-2] Scheme 1). Preferentially buffer solutions with
and 2-butyl-2-ethyl-1,3-propanediol [115-84-4] a pH 4 – 5 [19] or weak acidic ion exchange
(see Table 1) are produced either by the salt-free resins [20] are used as catalysts. Further hydro-
procedure based on aldol addition followed by genation of this aqueous solutions gives 1,3-
hydrogenation [16] or by the classical combi- propanediol [21]. There is an alternative route
nation of hydroxymethylation and Cannizarro- via hydroformylation of ethylene oxide and
type disproportionation with formaldehyde [17] subsequent hydrogenation of the intermediate
(see Scheme 1). 3-hydroxypropionaldehyde [22].
The production costs are considerably higher A new large market for 1,3-propanediol will
than for neopentyl glycol, since the synthesis be in polyester coatings and in the production of
of 2-methylpentanal and of 2-ethylhexanal from poly(trimethylene terephthalate), a new material
propanal and butanal requires two more steps: for the production of high quality carpet fibers
aldol condensation and hydrogenation. [23].
Since ca. 1980 2-butyl-2-ethyl-1,3-propane-
diol has become a very useful diol for polyester
or polyurethane coatings [18]. The world pro- 2.2.6. 2-Methyl-1,3-propanediol
duction of 2-butyl-2-ethyl-1,3-propanediol is es-
timated at about 10 000 t/a; the main producer is 2-Methyl-1,3-propanediol [2163-42-0] is a
Neste. fairly new commercially available diol and is
The best known fine chemicals produced produced by Arco with an estimated capacity of
from 2-methyl-2-propyl-1,3-propanediol are about 7000 t/a [24]. The process is designed for
the dicarbamates Meprobamate (β-methyl- the production of 1,4-butanediol [110-63-4] as
β-propyltrimethylene dicarbamate [57-53-4]), an alternative to Reppe technology and the ace-
used as a tranquilizer, and Carisoprodol (N- toxylation of butadiene.
isopropyl-β-methyl-β-propyl-trimethylene di- The raw material propylene oxide [75-56-9]
carbamate [78-44-4]), used as a muscle relaxant. is isomerized to allyl alcohol [107-18-6]
in the first step. Hydroformylation of al-
2.2.4. 2-sec-Butyl-2-methyl-1,3-propanediol lyl alcohol gives 4-hydroxybutanal (79 %)
[25714-71-0] and 3-hydroxy-2-methylpropanal
2-sec-Butyl-2-methyl-1,3-propanediol (see Ta- (11 %) [38433-80-6]. The last step comprises
ble 1) [813-60-5] can be made via 2,3- hydrogenation of the n and iso intermediates to
dimethylbutanal by simultaneous aldol addi- the corresponding diols. 2-Methyl-1,3-propane-
tion and Cannizzaro reaction with formalde- diol is used in polyester coatings.
hyde [25]. So far it has been used only in
the production of the tranquilizer Mebuta-
mate (β-sec-butyl-β-methyl-trimethylene dicar-
bamate [64-55-1]).
8 Alcohols, Polyhydric

2.3. 1,6-Hexanediol of esters, catalysts such as copper chromite or

copper with added zinc and barium are used as
1,6-Hexanediol [629-11-8], hexamethylene gly- “full catalysts” or on inert carriers [27], [28].
col, HOCH2 (CH2 )4 CH2 OH, colorless crystals Both acids and esters also may be hydrogenated
(see Table 1), is soluble in water and other polar using suspended catalysts.
solvents.

Production. 1,6-Hexanediol is produced in- Quality and Analysis. The assay of the
dustrially by the catalytic hydrogenation of pure product is about 98 %; impurities are var-
adipic acid or of its esters. Mixtures of dicar- ious diols and ε-caprolactone as well as traces
boxylic acids and hydroxycarboxylic acids with of water. The color number of the product deter-
C6 components formed in other processes (e.g., mined photometrically according to the Pt/Co
in cyclohexane oxidation) also can be used. scale must not exceed 15 APHA. Above 70 ◦ C,
The acids are hydrogenated continuously 1,6-hexanediol tends to turn yellow.
at 170 – 240 ◦ C and at 15.0 – 30.0 MPa (150 –
300 bar) on a suitable catalyst either in a trickle- Storage and Transportation. 1,6-Hexan-
flow (downflow) or a bubble-flow (upflow) ediol in the form of flakes or as a solidified
fixed-bed reactor. The reactor temperature is melt is stored and shipped in barrels. It is trans-
controlled by circulating part of the reactor dis- ported as a melt in stainless steel containers,
charge. The hydrogen required for the hydro- tank trucks, or tank cars.
genation is fed together with the recycle gas
through the recycle gas compressor to the re- Uses and Capacity. The most important use
actor (see Fig. 1). of 1,6-hexanediol is in the synthesis of
polyesters and polyurethanes. In addition it is
used in the production of varnishes, adhesives,
pharmaceuticals, and textile auxiliaries.
The world capacity of 1,6-hexanediol is ca.
25 000 t/a; manufacturers are BASF and Ube.

2.4. Hexynediols

2.4.1. 3-Hexyne-2,5-diol

3-Hexyne-2,5-diol [3031-66-1] is a more or less

solid yellow mass of crystals (see Table 1) de-
pending on the relative content of the meso form.
It is miscible with water and polar solvents.

CH3 CH(OH)-C≡C-CH(OH)CH3

3-Hexyne-2,5-diol is produced by BASF

from acetylene and acetaldehyde by the Reppe
Figure 1. Hydrogenation of adipic acid or of its esters ethynylation method (→ Acetylene). 3-Hexyne-
(trickle-flow fixed bed) 2,5-diol is used, for example, as a bright-
ener for nickel baths (80 % aqueous solu-
Side products of the synthesis are alcohols, tion) or as starting material for production
ethers, diols, and esters. Pure 1,6-hexanediol is of 2,5-hexanediol [28], but especially in the
obtained by fractional distillation of the crude production of 4-hydroxy-2,5-dimethyl-3-(2H)-
reactor discharge. furanone [3658-77-3], trade name Furaneol
For the hydrogenation of dicarboxylic acids, [29], used as pineapple and strawberry flavor.
catalysts containing cobalt, copper, or man-
ganese are suitable [26]. For the hydrogenation
 Alcohols, Polyhydric 9

2.4.2. 2,5-Dimethyl-3-hexyne-2,5-diol Production. 2,2-Bis(4-hydroxycyclo-

hexyl)propane is produced by hydrogenation
2,5-Dimethyl-3-hexyne-2,5-diol [142-30-3], of bisphenol A, 2,2-bis(4-hydroxyphenyl)pro-
(CH3 )2 C(OH)-C≡C-C(OH)(CH3 )2 , white pane [80-05-7], an industrially important com-
crystals (see Table 1), is produced by addition pound made from acetone and phenol (→ Phe-
of acetone to acetylene. It is an intermediate nol Derivatives). Bisphenol A is hydrogenated
of minor importance in the production of 2,5- at about 25.0 MPa (250 bar) and at 200 ◦ C on a
bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, nickel, cobalt, or ruthenium catalyst [31–33].
which is used as an initiator in polymeriza-
tion processes, as well as in the production of Uses. 2,2-Bis(4-hydroxycyclohexyl)pro-
moschus fragrances, of chrysanthemumic acid, pane is used mainly in synthetic materials as
and of surfactants (surfinols) by oxalkylation a bifunctional component, e.g., as a modifier
(Air Products). Manufacturers are Enichim and in the production of saturated and unsaturated
Air Products. polyester resins, and of oil- and fatty-acid-
containing alkyd resins. Exchange of hydroxyl
for amino gives a diamine which can be used in
2.5. 1,10-Decanediol the production of glass-clear polyamides.

1,10-Decanediol [112-47-0] (see Table 1) is pro-

duced from sebacic acid by a process analo- 2.7. 1,4-Bis(hydroxymethyl)cyclohexane
gous to that described for 1,6-hexanediol [30]
(see Section 2.3). It is an intermediate of minor 1,4-Bis(hydroxymethyl)cyclohexane [105-08-8]
importance in the production of polyesters and is commonly known as 1,4-cyclohexanedimeth-
polyurethanes. anol (CHDM), also as 1,4-dimethylolcyclo-
hexane, or hexahydro-p-xylylene glycol.
HOCH2 (CH2 )8 CH2 OH

Manufacturers are Ashland and Degussa-Hüls.

2.6. 2,2-Bis(4-hydroxycyclohexyl) The compound became known in the 1960s

propane mainly for its use in polyester films and fibers
highly resistant to hydrolysis.
2,2-Bis(4-hydroxycyclohexyl)propane [80-04-6]
is a crystalline, colorless, and odorless com- Physical Properties (see also Table 1). 1,4-
pound (see Table 1). Cyclohexanedimethanol is colorless and has a
slight odor. The softening point of the cis isomer
is 43 ◦ C, that of the trans isomer 67 ◦ C.
Cis – trans mixtures can be isomerized at 200 ◦ C
in the presence of alkoxides to an equilibrium
mixture of 42 % cis and 76 % trans. The com-
mercial product consists of a mixture of cis and
The conformation of the cyclohexane rings trans isomers with a typical ratio of 1/3.
gives rise to cis-cis, cis-trans and trans-trans iso- 1,4-Cyclohexanedimethanol is miscible with
mers. The industrial product is a mixture of these water as well as with low molecular mass alco-
stereoisomers. The physical properties depend hols; it is very slightly soluble in hydrocarbons
on the relative amounts of the isomers present. and ethers. Its solubility at 20 ◦ C (g in 100 g sol-
The trans-trans compound has the lowest energy vent) in benzene is 1.1, in trichloromethane 5.7,
and is formed from the other isomers at higher in water 92.0, and in methanol 92.2.
temperature. It has the lowest solubility in sol-
vents such as methanol, butanol, and acetone and
has the highest melting point of these isomers.
10 Alcohols, Polyhydric

Chemical Properties. CHDM undergoes hydrogenation. The crude DMHT of stage one
the characteristic reactions of a diol with two is used in a plant analogous to that of the first
primary hydroxyl functions. In contrast to 1,2- stage [40], although any conventional hydro-
and 1,3-diols reactions of CHDM with aldehy- genation plant can be used since the heat of the
des or ketones do not result in the formation of ester hydrogenation is comparatively small.
heterocyclic products, such as 1,3-dioxolanes or The industrial processes use commercial cop-
1,3-dioxenanes. per chromite catalysts. The effects of catalyst,
residence time, and temperature must be care-
Production. The commercially important fully adjusted in order to achieve a cis/trans ratio
process for producing CHDM is the hy- of 1/3 to 1/4 in the CHDM product.
drogenation of dimethyl terephthalate (DMT) A constant isomer ratio is important for fur-
[120-61-6]via dimethyl hexahydroterephthalate ther processing of CHDM in polyester formation
(DMHT) [94-60-0] in a methanolic solution or since the crystal structures of polyesters of cis-
in the molten state [34]: and trans-CHDM differ and thus influence the
melting range and density of polyester fibers.
In addition to the side products of the first
hydrogenation stage, 4-methyloxymethylhy-
droxymethylcyclohexane and bis(4-hy-
droxymethylcyclohexyl) ether can be formed
in the second stage of ester hydrogenation. The
Eastman process (see above) [34] avoids the
formation of high-boiling compounds and thus
saves cumbersome separation of side products
The hydrogenation plant consists of two reac- by fractionation in vacuum. The diol is purified
tors. In the first reactor, a continuous circulation by simply removing methanol and low-boiling
of product DMHT and of DMT is maintained. compounds. The CHDM of fiber quality ob-
The molten DMT is pumped into the inlet of tained by this method is ca. 99 % pure.
this reactor, which operates at 30 – 48 MPa and Pure CHDM may also be obtained by re-
160 – 180 ◦ C with a commercial supported Pd cycling waste poly(1,4-cyclohexylene dimethy-
catalyst. Temperature control is achieved by op- lene terephthalate) by first cleaving the polyester
erating at sufficiently high cross-sectional load- in the presence of low molecular mass alcohols
ings of the mixture of ca. 10 % in product and then subjecting the resulting mixture to a hy-
DMHT. This allows the radial dissipation of heat drogenation analogous to that described above
via the reactor walls and largely avoids high [35]. Estimated world capacity is 55 000 t/a.
temperature peaks. The cooled reactor effluent,
which contains only minor amounts of unreacted Uses. An important application of CHDM is
DMT, is divided: 8 – 10 parts are recycled via still the production of terephthalate – polyester
a pump and heat exchanger to the reactor inlet. fibers with lower densities and higher melting
The remaining 1 – 2 parts (the exact amount cor- points than analogous fibers using ethylene gly-
responds to the amount of fresh DMT) are fed col. They are more stable to hydrolysis and have
continuously into the second reactor for the final more favorable electrical properties than similar
Pd-catalyzed hydrogenation. polyesters made from other diols [35].
An advantage of this process is that DMT can Unsaturated resins based on CHDM are char-
be hydrogenated as ca. 10 % dilute feed with- acterized by very good properties with re-
out handling large amounts of liquid. The yield spect to water absorption, thermal stability,
of DMHT is typically 97 – 98 %, with methyl and resistance to environmental and chem-
4-methyl-4-cyclohexanecarboxylic acid methyl ical exposure [36]. The use of CHDM in
ester [51181-40-9] and some 1-hydroxymethyl- saturated polyester resins leads to powder,
4-methylcyclohexane [34885-03-5] as main waterborne, and solvent-based coatings with
byproducts. excellent hardness and durability [37]. 1,4-
1,4-Bis(hydroxymethyl)cyclohexane Cyclohexanedimethanol is of increasing inter-
(CHDM) is formed in the second stage of the est for application in polyurethanes and poly-
 Alcohols, Polyhydric 11

carbonates [38] as well as an antifogging agent 2.9. Vicinal Diols by Hydroxylation of

and as a sensitizing additive in silver bromide Olefins with Peracids
emulsions.
Some vicinal diols are manufactured on a com-
mercial scale by the reaction of an alkene with
2.8. 2,2,4-Trimethyl-1,3-pentanediol an organic peracid, such as performic acid, pro-
duced in situ, or peracetic acid [41]. An epoxide
2,24-Trimethyl-1,3-pentanediol [144-19-4], is formed initially; acid-catalyzed cleavage of
TMPD glycol, is a white crystalline solid (see the epoxide ring leads to a 1,2-diol or a 2-hy-
Table 1). It is a versatile diol with a wide droxyalkyl-ester or a mixture of the two. The 2-
range of applications including polyester resins, hydroxyalkyl ester is hydrolyzed to the 1,2-diol
polyurethane foams, and lubricants. by the subsequent treatment with a base.

2.9.1. 1,2-Pentanediol

1,2-Pentanediol [5343-92-0], 1,2-dihy-

droxypentane, CH3 (CH2 )2 CH(OH)CH2 OH, is
a colorless and odorless liquid which is miscible
Physical and Chemical Properties. TMPD with water and polar organic solvents (see also
glycol is only slightly soluble (< 2 %) in water Table 1).
and kerosene, but very soluble (up to 80 %) The compound is made by treating a mixture
in alcohols. The solubility in benzene, acetone, of 1-pentene and formic acid with 40 % hydro-
and ethers is at most 29 %. gen peroxide at 30 ◦ C [42]. 1,2-Pentanediol has
TMPD glycol, with one primary and one sec- attained commercial importance as a synthetic
ondary hydroxyl function, shows the typical re- building block for systemic fungicides [43] and
activity of a diol. In comparison to other diols, as a moisturizing agent in cosmetics.
such as CHDM (see Section 2.7) or NPG (see
Section 2.2.1), TMPD glycol has an unsymmet-
rical structure and shielded hydroxyl groups. 2.9.2. Other 1,2-Diols

Production. TMPD glycol is produced by Pinacol [76-09-5], 2,3-dimethyl-2,3-

homo-aldol condensation of isobutyraldehyde butanediol, (CH3 )2 C(OH)C(OH)(CH3 )2 , col-
[78-84-2] in the presence of an alkaline cata- orless crystals, is soluble in hot water, alcohol,
lyst followed by hydrogenation of the resulting and ether and slightly soluble in cold water and
cyclic acetal to give TMPD glycol and isobu- carbon disulfide. The hexahydrate, mp 45 ◦ C,
tanol. Eastman Chemical is the only manufac- crystallizes as four-sided plates (see also Ta-
turer of TMPD glycol. ble 1).

Uses. TMPD glycol is mainly used as raw 1,2-Hexanediol [6920-22-5], (bp 108 ◦ C/0.5
material in the production of unsaturated and hPa;  0.953 g/cm3 at 20 ◦ C) is a colorless liq-
saturated polyesters (e.g. for waterborne or uid miscible with water. It is used in printing
high-solids coatings) and as an intermediate inks and in cosmetics.
for polyesters used in the manufacture of
polyurethane elastomers and foams [39]. These 1,2-Octanediol [1117-86-8] (bp 140 ◦ C/1.6
resins are very stable to hydrolysis and resistant hPa) is a white waxy solid, slightly soluble in
to corrosion, as well as having other desirable water. Its production is described in [42], [44].
features, such as low density, low viscosity, and It is used in printing inks and in cosmetics.
good compatibility.
12 Alcohols, Polyhydric

3. Triols distilled. The removal of discoloring impurities

is described in [55].
3.1. Trimethylolpropane Cyclic diethers of the acetal type (1,3-
dioxanes, formals) can be converted into TMP
Properties. Trimethylolpropane [77-99-6], and methanol by metal-catalyzed hydrogenation
2-ethyl-2-hydroxymethyl-1,3-propanediol, [56].
CH3 CH2 C(CH2 OH)3 , is a colorless, crystalline,
trivalent alcohol (see Table 1). Trimethylolpro- Uses. Large quantities of trimethylolpropane
pane is quite soluble in water and polar organic and its ethoxylated derivatives are used as
solvents. The three primary hydroxyl groups precursors for urethanes and polyester resins.
undergo the normal OH group reactions. Another important field of application is in
medium-oil and short-oil alkyd resins (→ Alkyd
Production. Trimethylolpropane is made by Resins). The resulting lacquers are characterized
the base-catalyzed aldol addition of butyralde- by excellent resistance to alkali, detergents, and
hyde with formaldehyde followed by Canniz- water, combined with outstanding impact resis-
zaro reaction of the intermediate 2,2-bis(hy- tance and flexibility, as well as excellent clear-
droxymethyl)butanal with additional formalde- ness and clearness retention.
hyde and at least a stoichiometric quantity of Reaction products with fatty acids (C5 – C10 )
base (see Scheme 1): are components of synthetic lubricants. A
strongly growing market will be the use of these
blended polyol esters in chlorine-free, purely
fluorocarbon based refrigerant systems. Powder
and high-solids coatings represent a strong po-
tential market for TMP, because it contributes to
low viscosity. TMP acrylates are used as reac-
tive diluents in UV-cured systems for inks and
coatings, and TMP allyl ethers in unsaturated
Sodium hydroxide [45], [46] or calcium hydrox- polyesters.
ide [47], [48] are used as bases in industrial-
Economic Aspects. World production ca-
scale production. The yield in both cases is
pacity for trimethylolpropane was estimated at
ca. 90 %. Many attempts have been made to
150 000 t in 1998, of which about 67 000 t was
avoid the large quantities of formate byproduct
accounted for by Western Europe, 60 000 t by
by catalytic hydrogenation of the 2,2-bis(hy-
the United States, and 15 000 t by Japan. The
droxymethyl)butanal [49], [50]. These pro-
main producers are Bayer, Perstorp, and Polioli
cesses have been achieved by using tertiary
in Western Europe; Celanese and Perstorp in the
amines as catalyst and transforming the formed
United States; and Koei and Mitsubishi Gas in
ammonium formate into methyl formate [87] or
Japan.
even avoiding the formation of larger amounts
of formates [88].
Various procedures have been suggested for
separating the trimethylolpropane from the for- 3.2. Trimethylolethane
mate. For instance, the concentrated reaction Properties. Trimethylolethane [77-85-0],
solution can be extracted with an organic sol- 2-hydroxymethyl-2-methyl-1,3-propanediol,
vent, which is then evaporated and the crude CH3 C(CH2 OH)3 , is a colorless, crystalline sub-
trimethylolpropane is purified by vacuum dis- stance (see Table 1), soluble in water (140 g per
tillation [51], [52], [53]. In another variant 100 g at 25 ◦ C), alcohols, and acetone.
[54], the aqueous reaction solution is evapo-
rated until most of the sodium formate crystal- Production. Trimethylolethane is made by
lizes and is removed by hot filtration. The liquid aldol condensation of propionaldehyde with
trimethylolpropane which remains is liberated formaldehyde, followed by reaction of the inter-
of residual salts with an ion exchanger and then mediate 2,2-bis(hydroxymethyl)propanal with
 Alcohols, Polyhydric 13

excess formaldehyde in the presence of sodium 4.2. Pentaerythritol

hydroxide or lime as basic component (see
Scheme 1). Pentaerythritol [115-77-5], 2,2-bis(hy-
droxymethyl)-1,3-propanediol, C(CH2 OH)4 ,
H3 CCH2 CHO + 3 H2 CO + NaOH was discovered by Tollens in 1882 when an
−→ H3 CC(CH2 OH)3 + HCOONa aqueous solution of formaldehyde containing
The resulting aqueous solution is freed from ex- some acetaldehyde was allowed to stand with
cess formaldehyde by distillation under pressure barium hydroxide [59].
and further concentrated. The formate byprod-
uct can be separated by extracting the trimethy- Properties. Pentaerythritol is a colorless,
lolethane from the residue with organic sol- crystalline alcohol with four primary hydroxyl
vents such as 2-propanol [57] or by almost com- groups. It crystallizes in a tetragonal system
plete removal of the water and dissolving the with. The tetragonal crystals convert into the
trimethylolethane in acetone or methanol. cubic form at 180 – 190 ◦ C. The compound sub-
limes on heating in vacuum without dissociation.
Uses and Economic Aspects. Trimethylo- Important physical data are listed below (see also
lethane, like trimethylolpropane, is a polyol Table 1):
component of short- and medium-oil alkyd Heat of combustion ( p = const.) 2767 kJ/mol
resins, in which it results in a shorter drying time Heat of formation 931 kJ/mol
and, because of its shorter alkyl chain, a harder Specific heat capacity at 100 ◦ C 255 J/mol
Ignition temperature 390 ◦ C
lacquer film compared with trimethylolpro- Solubility in water (per 100 g water)
pane. However, its economic importance is at 25 ◦ C 7g
at 97 ◦ C 77 g
small compared with that of pentaerythritol or
trimethylolpropane. It is produced by Mallinck-
rodt (USA) and Mitsubishi Gas (Japan) in Mixtures of air and pentaerythritol dust are ex-
amounts of several thousand tonnes per annum. plosive at 490 ◦ C and at dust concentrations
of more than 30 g/m3 . The four primary hy-
droxyl groups undergo the normal reactions
4. Tetrols of OH groups [60]. Pentaerythritol is oxidized
to tris(hydroxymethyl)acetic acid by air in the
4.1. Ditrimethylolpropane presence of platinum or palladium [61].

Ditrimethylolpropane [23235-61-2] 2,2- Production. Pentaerythritol is prepared by

[oxybis(methylene)]-bis(2-ethyl)-1,3-propane- the reaction of acetaldehyde with formaldehyde
diol is a colorless and crystalline substance (mp in alkaline medium. The aldol addition results
112 – 114 ◦ C), only slightly soluble in water at in replacement of the three α-hydrogen atoms,
ambient temperature (2.6 g/100 g at 25 ◦ C). leading to trimethylolacetaldehyde (pentaery-
throse), which is reduced to pentaerythritol by
excess formaldehyde in the presence of base
(sodium hydroxide or calcium hydroxide). The
yield is approximately 90 %. Catalytic hydro-
genation of pentaerythrose, which would avoid
It is a byproduct of TMP production and can the formate byproduct, is not practicable. Higher
be isolated from the residue of the TMP dis- homologues of pentaerythritol with the general
tillation step. Newer investigations show that formula
ditrimethylolpropane can be prepared in high
yield and selectivity by the reaction of TMP,
formaldehyde, and 2-ethylacrolein [58]. It is
used in water-thinnable alkyd resins and as a
polyol component in PVC stabilizers based on
Ca/Zn alkyl carboxylates. Producers are Per-
storp (Sweden) and Mitsubishi Gas (Japan). are byproducts of the production of pentaery-
14 Alcohols, Polyhydric

thritol. The product with n = 2, known as dipen- and medium-oil alkyd resins. The pentaerythri-
taerythritol, is the primary contaminant. To min- tol structure gives the resin outstanding prop-
imize its formation it is necessary to increase the erties both in processing and end use. Resins
ratio of formaldehyde to acetaldehyde beyond prepared from pentaerythritol and rosin or tall
the stoichiometric ratio of 4:1 [60]. Addition- oil are used for the modification of printing inks
ally, certain amounts of formaldehyde acetals and nitrocellulose lacquers and for the prepa-
are formed [62]. Both batch and continuous ration of adhesives and core binders. Solvent-
processes for the production of pentaerythritol free, water-thinnable alkyd resin emulsions can
have been described [63], [64]. be prepared by using tribasic acids in the ester-
To isolate the product, the aqueous reaction ification process, which gives water-dispersible
solution is first freed of excess formaldehyde and salts after neutralization.
most of the water by distillation under pressure. Pentaerythritol esters of short- to medium-
After further concentration, usually in vacuo, the chain carboxylic acids (C5 – C10 ) are applied as
crude pentaerythritol crystallizes. The mother high-temperature synthetic lubricants, lubricant
liquor contains the sodium formate plus resid- additives, and plasticizers. An emerging market
ual pentaerythritol. Separation of the formate, for these esters is as refrigerant lubricants. Be-
recycling of the residual pentaerythritol, and cause of the ozone-depleting properties of CFCs
elimination of the wastewater occur in subse- they are to be replaced by chlorine-free fluoro-
quent process steps. The crude pentaerythritol carbons. However, since this class of compounds
is purified by recrystallization from water after differs in polarity the compressor must be lubri-
treatment with activated carbon. By using lime, cated with oils of higher polarity [68], [69] Pen-
the process runs reversely; first calcium formate taerythritol tetranitrate is used as a detonator in
separates because of its low water solubility, the fuses and, to a limited extent, as a military ex-
mother liquor than contains the dissolved pen- plosive. The tetranitrate also is used in medicine
taerytrithol. Residual Ca2+ or Na+ ions can be as a long-term coronary vasodilator.
removed by ion-exchange resins. The wastewa- Finely ground pentaerythritol in combination
ter contains a certain amount of dissolved pen- with metal soaps serves as a nontoxic costa-
taerythritol, which can be recovered [65]. bilizer for poly(vinyl chloride). It also is used
in flame retardant compositions (intumescent
Quality and Analysis. Pentaerythritol is paints). Under the action of heat an insulating
available in various grades which differ in their foam layer forms, up to 50 times the thickness
content of the above-mentioned byproducts in- of the original coating. Pentaerythritol triacry-
cluding residual ash (alkali metal salts and/or late is used as an active diluent in radiation-
alkaline earth metal salts). Higher ash content cured paints. Pentaerythritol adducts with ethy-
often has a detrimental effect on the color of the lene oxide are used as emulsifiers, inorganic
alkyd resin obtained from the product. Products phosphoric or phosphoric esters are used as ad-
termed pentaerythritol monograde generally ditives in hydraulic fluids, and tetraesters with
contain more than 97 % pentaerythritol, whereas sterically hindered phenylcarboxylic acids act
the technical grade consists of 80 – 95 % pen- as a highly effective antioxidant in plastics.
taerythritol and 5 – 15 % dipentaerythritol.
For quality control, the melting point, hy- Economic Aspects. In 1998, world produc-
droxyl number, ash content, and the color tion capacity was estimated to be 360 000 t,
or iodine number of the melt are deter- 71 000 t of which was in the United States,
mined. Gas chromatographic analysis after 120 000 t in Europe, 27 000 t in Japan, and
silylation with agents such as N-methyl-N- 25 000 t in Canada. Smaller producers are lo-
trimethylsilyltrifluoracetamide [66] gives pre- cated in many other countries. The main man-
cise information on the composition of the ufacturers are Perstorp, Hoechst-Celanese, and
sample. Analysis by high-pressure liquid chro- Degussa-Hüls. The overall pentaerythritol mar-
matography has also been described [67]. ket is expected to grow at a rate of 1.5 – 2 %/a.
The alkyd resin market should be stable, and
Uses. The major application of pentaerythri- growing use of fatty acid esters in refrigerant
tol (ca. 70 %) is the production of long-oil systems can be assumed.
 Alcohols, Polyhydric 15
Table 2. Lethal doses of polyhydric alcohols (in mg/kg)
alkyd resins with low viscosity (high solids), and
1,4-Butanediol [25265-75-2] [73], [74] as a nonsubliming polyol component in nontoxic
LD50 1500 – 1780 (rat, oral) PVC stabilizer systems.
1,2-Butanediol [584-03-2] [73]
LD50 16000 (rat, oral)
The total installed capacity is ca. 6000 t. Main
1,3-Butanediol [107-88-0] [75], [76] producers are Hercules, Koei, Perstorp, Polialco,
LD50 29600 (rat, oral) and Degussa-Hüls.
1,5-Pentanediol [111-29-5] [77]
LD50 5890 (rat, oral)
1,6-Hexanediol [629-11-8] [77]
LD50 3730 (rat, oral) 5.2. Tripentaerythritol
2,5-Hexanediol [2935-44-6] [77]
LD50 5000 (rat, oral) Tripentaerythritol [78-24-0], 2,2-bis[hydroxy-
LD50 16 000 (rabbit, dermal)
1,2-Hexanediol [6920-22-5] 2,2-bis(hydroxymethyl)propoxy]methyl-1,3-
LD50 > 5000 (rat, oral) propanediol is only slightly soluble in cold and
1,2-Octanediol [1117-86-8] hot water and can be isolated during the produc-
LD50 2200 (rat, oral)
1,3-Propanediol [504-63-2] tion of dipentaerythritol. It has at present only a
LD50 15670 (rat, oral) very limited economic importance.
2,2,4-Trimethyl-1,3-pentanediol,
(TMPD glycol) [144-19-4] [79]
LD50 2000 (rat, oral),
LD50 145 (rat, intravenous) 6. Toxicology
Neopentyl glycol [126-30-7]
LD50 6400 – 12800 (rat, oral) [81] Table 2 summarizes the acute toxicity data of
1,4-Bis(hydroxymethyl)cyclohexane
(CHDM )[105-08-8] [77], [80]
polyhydric alcohols. According to the lethal
LDo 3200 (rat, oral) doses shown, these compounds are generally lit-
LDo 1600 (mouse, oral) tle toxic. For comparison, the LD50 values of the
Pentaerythritol [115-77-5]
LDo > 5110 (rat, oral) [83] butanediols also are included in Table 2.
LD50 19 000 (mouse, oral) [84]
Dipentaerythritol [124-58-9] TMPD Glycol, 2,2,4-trimethyl-1,3-pen-
LD50 > 2000 (rat, oral)
Trimethylolpropane [77-99-6] [82]
tanediol, is classified as “slightly toxic” [78],
LD50 14100 (rat, oral) [79], see Table 2. In rabbits, moderate eye irri-
tation was observed. Slight to no skin irritation
occurred in guinea pigs, and no skin sensitization
was found. Repeated skin application studies in
5. Higher Polyols humans gave no evidence of irritation, sensi-
tization, photosensitization, or systemic toxic
5.1. Dipentaerythritol effects. In humans, TMPD glycol is rapidly
excreted in the urine, partly unchanged, partly
Dipentaerythritol [126-58-9], 2,2-[oxybis(meth- as the glucuronide and sulfate conjugates, and
ylene)-bis[2-hydroxymethyl]-1,3-propanediol, partly as 2,2,4-trimethyl-3-hydroxyvaleric acid.
is a byproduct of pentaerythritol production. Be-
cause of its low solubility in water (0.22 g/100 g 1,4-Bis(hydroxymethyl)cyclohexane
H2 O at 20 ◦ C and 10.0 g/100 g H2 O at 100 ◦ C) (CHDM) has a low acute toxicity (see Table 2).
it can be separated from pentaerythritol by frac- For metabolism of CHDM in rats, see [80].
tional crystallization. The yield can be increased Trimethylolpropane is practically nontoxic
by changing the ratio of formaldehyde/acetalde- (see Table 2). Skin irritation was not observed.
hyde towards stoichiometric. Adding pentaery-
thritol before starting the reaction also increases Pentaerythritol is practically nontoxic.
the yield. An effective method is to use acrolein Health disturbances resulting from handling
instead of acetaldehyde [70], [71]. pentaerythritol have never been observed. High
In the last decade the consumption of dipen- oral doses (50 g) administered to humans re-
taerythritol steadily increased. The main out- sulted only in slightly increased pulse rate [85].
lets are C5 – C10 ester lubricants for jet en- Diarrhea was observed at high doses in ani-
gines and refrigerator systems [72], dipentahex- mals. Pentaerythritol is readily biodegradable
aacrylate as cross-linking agent for UV-curing under aerobic conditions according to OECD
acrylates, for water-resistant intumescent paints, Guideline No. 301 [86].
16 Alcohols, Polyhydric

1,2-Diols. The oral LD50 values in rats for Lappe, H. Springer, F. Thoennessen). Aristech,
1,2-hexane-diol, 1,2-octanediol, are included in US 5 146 012, 1991(J. S. Salek, J. Pugach,
Table 2. For these 1,2-diols, skin irritation was C. L. Carole, L. A. Cullo). Mitsubishi Gas
not observed in rabbits. 1,2-Octanediol caused Chemical, EP 708073, 1994(T. Nimomiya, T.
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Aldehyde Polymers → Polyoxymethylenes