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Polyols – more than sweeteners
Polyole – mehr als Süßungsmittel
Michael A. Radeloff and Roland H.F. Beck
1 Introduction
Polyols are saccharide derivatives in which the carbonyl group
has been reduced to a hydroxyl group, therefore also named
“sugar alcohols”. Commercially available polyols extend from
sorbitol, mannitol, maltitol, isomalt, xylitol, and lactitol to
erythritol.
e traditional food use of sugar alcohols as low caloric sweet-
eners carrying a “sugar-free” claim often is combined with
high intensity sweeteners to make up for the lower sweetness
of sugar alcohols in comparison to sugar [1]. Sugar alcohols are
slowly and incompletely absorbed into the blood stream from
the small intestines [2], which generally results in a smaller
change in blood glucose than sucrose. e resulting low glyce-
mic index explains the interest for sugar alcohols in diabetic
foods [3]. As polyols are not fermentable by oral bacteria they
do not contribute to tooth decay [4]. Other functional proper-
ties include a pleasant cool taste and the physical, chemical
and microbiological stability over a wide range of pH and
temperatures, which make polyols a valuable food ingredient.
Beyond sweetness, sorbitol has become a bulk chemical intro-
ducing an element of sustainability in a world of petrochemi-
cals.
1.1 e market environment
Polyol production is controlled by a few international play-
ers but new producers in emerging economies are gaining
Polyols – produced today at a millions of tons scale by hydro-
genation or fermentation of carbohydrates from renewable
raw materials – have become a valuable “natural” ingredient
in a wide range of applications in the food, cosmetics, phar-
maceutical, chemical and technical industry. Beyond sweet-
ness at low calorific value and favourable glycemic response,
the intrinsic properties of polyols make them versatile and
widely used bulking agents, humectants, binders, complex-
ing agents, plasticizers and chemical reactants, whenever
“green chemistry” solutions are looked for.
Key words: polyol, sugar alcohol, sorbitol, mannitol, maltitol,
isomalt, xylitol, lactitol, erythritol
Polyole werden heute im Millionen-Tonnen-Maßstab durch
Hydrierung oder Fermentation von Kohlenhydraten aus
nachwachsenden Rohstoffen hergestellt. Sie sind zu wert-
vollen „natürlichen“ Zusatzstoffen mit breitem Anwen-
dungsbereich in der Lebensmittel-, Kosmetik-, pharmazeu-
tischen, chemischen und technischen Industrie geworden.
Nicht nur als Süßungsmittel mit geringem Kaloriegehalt
und niedrigem glykämischem Index sind Polyole dank ihrer
spezifischen Eigenschaften zu vielseitigen und viel verwen-
deten Füllstoffen, Feuchthaltemitteln, Bindemitteln, Kom-
plexbildnern, Weichmachern und chemischen Ausgangsstof-
fen geworden, und zwar überall dort, wo Lösungen im Sinne
einer „grünen Chemie“ gesucht werden.
Schlagwörter: Polyol, Zuckeralkohol, Sorbit, Mannit, Maltit,
Isomalt, Xylit, Laktit, Erythrit
Table 1: Estimated worldwide
consumption of polyols
Polyol Consumption
in t
Sorbitol 800,000
Xylitol 200,000
Mannitol 180,000
Maltitol 160,000
Isomalt 80,000
Erythritol 50,000
influence. Controlling the
raw material costs is a key
economic success factor as
well as economy of scale in
production.
e worldwide consumption
of polyols is estimated at
close to 1.5 mn t (Table 1).
More than half of worldwide
polyols production is used in
food applications. However,
about three quarters of sorbitol production is consumed by
non-food applications.
1.2 Legal limitations of food use
e United States Food and Drugs Administration (FDA) con-
siders sugar alcohols as either “generally recognized as safe
(GRAS)” or approved food additives [5].
e European Food Additives List includes: sorbitol (E420),
mannitol (E421), isomalt (E953), maltitol (E965), lactitol
(E966), xylitol (E967), and erythritol (E968) [6].
When consumed in excessive amounts, sugar alcohols can
cause diarrhoea when non-absorbed amounts of sugar alcohols
are entering in the large intestine where they bind water and
are subject to fermentation resulting in a laxative effect, flatu-
lence and diarrhoea. erefore, laxative warning is required for
all foods containing more than 10% added polyols [7].
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2 e group of polyols
All polyols are derived from renewable
agricultural raw materials, which pro-
vide them with a “natural” and “green”
image (Fig. 1).
2.1 Production of polyols
Production processes for polyols gen-
erally are based on high-pressure cata-
lytic hydrogenation of the appropriate
carbohydrates. For reasons of flexibil-
ity in operation, batch process reactors
operated at 25–50 bar are the preferred
option over continuous process reactors
operated at 100–200 bar.
The hydrogenation reaction is per-
formed in the presence of Raney-nickel
or Ruthenium/carbon catalysts during
several hours in stirred vessels at tem-
peratures of 100 to 200 °C. Suspended
Raney-nickel is the preferred active cata-
lyst operated batch-wise at 40–50 bar
while Ruthenium mounted on a carbon
carrier is operated at somewhat lower
pressure [8].
e hydrogenated solution is decanted
Fig. 1: Natural origin of polyols
and filtered and the catalyst recycled and reused. After ion
exchange and carbon treatment the liquor is evaporated to
commercial standards or can be crystallized into powders of
specific physical characteristics (Fig. 2).
2.2 Physical and functional characteristics of
polyols
The combination of rather unique properties explains the
interest in polyols not only as low caloric sweeteners [9].
2.2.1 Relative sweetness
Relative sweetness is measured in relation to sucrose, which
has a reference value of 1.0 or 100%. Generally polyols vary
from less than half as sweet (lactitol 40%) to equally as sweet
as sucrose (xylitol 100%) (Fig. 3).
2.2.2 Food energy content
Despite the variance in food energy content of polyols, EU
labelling requirements assign a blanket value of 2.4 kcal/g,
a reduction of 40% compared to sucrose. Real values vary
from 2.6 kcal/g for sorbitol to 1.6 kcal/g for mannitol and
even 0.2kcal/g for erythritol in comparison to 4.0 kcal/g for
sucrose (Fig. 4).
Fig. 2: Production of polyols
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2.2.3 Glycemic index (GI)
e glycemic index reflects how quickly blood sugar levels rise
after ingestion of carbohydrates relative to the consumption
of pure glucose (GI = 100). e GI of polyols varies from 0 to
35 (Fig. 5).
2.2.4 Cooling effect
All crystalline polyols exhibit a negative heat of solution and
therefore provide a cooling sensation in the mouth. Values
vary from –43 cal/g for erythritol to –6cal/ for maltitol (Fig. 6).
2.2.5 Solubility in water at 20 °C
Sorbitol, xylitol, maltitol and lactitol are highly soluble in
water (50–70 g/100 g) but erythritol, isomalt and mannitol
are less (15–30 g/100 g) (Fig. 7).
2.2.6 Hygroscopicity
Water absorption from the atmosphere varies strongly from
highly hygroscopic sorbitol to non-hygroscopic mannitol and
erythritol (Fig. 8).
Fig. 3: Relative sweetness of commercial polyols
Fig. 4: Relative food energy content of commercial polyols
Fig. 6: Relative cooling effect of commercial polyols
Fig. 5: Glycemic Index of commercial polyols
Fig. 8: Relative hygroscopicity of commercial polyols
Fig. 7: Solubility (g/100 g) of commercial polyols in water at 20°C
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2.2.7 Polyol stability
Polyols are stable within a wide pH range of 2–10, they are
melting without decomposition, show no browning by Mail-
lard reaction and are heat stable up to 150–216 °C. (XYL > LAC
> MAN = ISOM = ERY > SORB > MAL)
2.2.8 Metal complexation
Polyols can bind metal ions such as Fe, Cu, Co, Ni, Mg, Ca and
Al under alkaline conditions.
3 Single polyols: Characteristics and use
Choosing the right polyol for a given application depends on
selecting the functional characteristics of the different polyols
that best fit to the intended use.
3.1 Sorbitol
Sorbitol is commercially produced from starch by enzymatic
saccharification yielding a corn syrup of high dextrose equiva-
lent (DE) that subsequently is subjected to catalytic hydroge-
nation (Fig. 9).
3.1.1 Product characteristics
Sorbitol syrups are characterized in terms of quality by the
sorbitol content and the remaining low level of reducing sug-
ars that can be responsible for undesired browning during
storage or further processing. Syrups of high sorbitol purity
are crystallizing easily and therefore need to be stored and
handled at elevated temperatures. Syrups containing small
amounts of other polyols, as a result of a carefully steered
starch saccharification process, do not crystallize and are the
product of choice for most applications.
Sorbitol powder has four crystalline structures – four anhy-
drous crystalline phases plus the hydrate. It may be crystal-
lized from an aqueous solution or low moisture melts or even
spray-dried/spray-crystallized. e g-polymorph is the most
stable of the anhydrous crystal forms used extensively in sug-
arfree confections and chewable tablets [10].
3.1.2 Food and non-food applications [11]
Food applications: Sorbitol introduces a smooth mouth feel
with a sweet, cool and pleasant taste and exhibits good taste
masking properties. It is about 60% as sweet as sucrose with
quite a strong negative heat of solution (–27 cal/g). The
low nutritive value of 2.6 kcal/g and the very low glycemic
response of only 9% that of glucose makes it an ideal ingredi-
ent in dietary foods, including dietary drinks and ice cream,
mints and sugar free chewing gum. Acting as a cryoprotectant
and humectant, sorbitol can protect against damage from
freezing and drying as in the manufacture of surimi, enzymes
or sensitive biotechnology drugs [12].
Pharmaceutical applications: Liquid sorbitol is used for taste
masking and as a bulking agent to add body and viscosity to
liqid dosage forms. Used as a shelf life extender, sorbitol acts
as a crystal modifier and inhibitor preventing syrups from
forming crystals of sugar. Sorbitol powder shows good com-
pressibility and is used as a binder or bulking agent in direct
compression tabletting and also in industrial tablets of deter-
gents.
Tobacco and cosmetics: Sorbitol, as the most hygroscopic of all
sugar alcohols, is used as a humectant where it finds itself in
hard competition with propylene glycol and glycerine. Other
applications in cosmetics and oral care include toothpaste,
mouth wash and breath freshener. In skin care it retains mois-
ture, provides clarity and translucency as it has a high refrac-
tive index close enough to the components of transparent
soap bars and translucent gels.
Technical applications of sorbitol include the use in alumin-
ium etching when the metal surface is treated in hot sodium
hydroxide solution for the creation of a perfectly lease and
matte surface finish. Sorbitol acts as a stabilizer to the etching
solution preventing the formation of rock-hard alumina scale
in the treatment tanks. e use of sorbitol as a plasticizer in
thermoplastic starch is based on its high affinity to starch, the
low migration tendency, good water retention and prevention
of starch crystallization [13].
3.1.3 Sorbitol as a key chemical intermediate
Sorbitol is an important starting material in the chemical
production of ascorbic acid (vitamin C), for polyether polyols
in polyurethane production, for sorbitan ester types of surfac-
tants and for isosorbide derivatives.
e historical Reichstein process to produce vitamin C from
glucose used sorbitol as an intermediate to produce sorbose
by fermentation and further chemical transformation into
ascorbic acid (Fig. 10). Today’s industrial process uses a second
fermentation step to form 2-ketogulonic acid (2-KGA) that
is chemically rearranged into vitamin C. Extensive research
is run to engineer a mutant which can carry out a one-pot-
fermentation directly from glucose to 2-KGA [14].
In sorbitol two primary and four secondary hydroxyl groups
are available for esterification or etherification reactions.
Fig. 9: Hydrogenation of glucose to sorbitol
Sorbitol acts as a polyalcohol when
reacted with dicarboxylic acids or their
anhydrides to form polyesters such as in
alkyds, the dominant resin for coatings
and paints [15] (Fig. 11).
e sorbitol functionality of six hydroxyl
groups makes it a starter molecule in
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Sorbitan ester surfactants (Fig. 14) can
cover a wide range on the hydrophilic-
lipophilic balance scale (HLB-value) by
varying the lipophilic fatty acid reactant
(Span-type surfactant) or extending the
hydrophilic sorbitan functionality by
ethoxylation (Tween-type surfactant).
Applications therefore include the whole
range of surfactant action as defoamers,
emulsifiers, wetting agents and deter-
gents. As sorbitan esters hardly show
any toxicity or irritancy they are widely
used in foods, personal care products or
textile care [17].
Isosorbide offers two hydroxyl groups
to form esters or ethers. Isosorbide
mono- and dinitrate are used as phar-
maceutical actives to treat angina pec-
toris. Isosorbide diester with 2-ethyl-
hexanoic acid can replace toxic phthal-
ates used as plasticizers in PVC. Isosor-
bide as a co-starter in polyether polyols
improves the stability in terms of heat,
pH and colour. The use of isosorbide
to form a copolymer of ethylene there-
phthalate (PET) (Fig. 15) introduces a
higher glass transition temperature and
thus a higher degree of rigidity into this
plastic [18].
3.2 Mannitol
Mannitol, the sugar alcohol stereoiso-
mer of sorbitol, can be obtained from
Fig. 10: Production of vitamin C from sorbitol
Fig. 11: Sorbitol in alkyd resin production
polyether polyol produc-
tion (Fig. 12), a compo-
nent that is reacted with
isocyanate to form rigid
polyurethane foams, the
thermosetting plastic
used extensively, e.g.
in automotive parts or
building insulation [16].
3.1.4 Sorbitan and
isosorbide
Sorbitan (anhydrosorbi-
tol) and isosorbide (dian-
hydrosorbitol, DAS) are
formed by heating a melt
of sorbitol under acidic
conditions and evaporat-
ing the water resulting
from a simple or twofold
dehydration reaction
(Fig. 13).
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Glucose can as well be epimerised to
mannose that chromatographically is
enriched and hydrogenated to mannitol
[20].
Mannitol-extraction of seaweed by
use of ethanol is commercially done
in China. Extraction of olive leaves by
use of supercritical CO2 or supercriti-
cal water is proposed. Biological synthe-
sis by fermentation can produce much
higher mannitol yields, with minimal to
no side products but is not yet commer-
cially exploited [21].
Mannitol, mildly acidic in aqueous solu-
tion, exhibits sweetness equal to glucose
and half as sweet as sucrose with a cool-
ing effect of –29 cal/g similar to sorbitol.
Mannitol shows a food energy value of
only 1.6 kcal/g but no glycemic response
at all. It virtually is non-hygroscopic
which makes it the polyol of choice in
coatings of hard candies, dried fruits,
and chewing gum [22].
In pharmaceutical applications mannitol
is used as a carrier in tablet and capsule
formulations. It is the preferred excipient
for chewable tablets due to its favourable
mouthfeel. In conventional tablets its
inertness and non-hygroscopic proper-
ties can protect sensitive actives. While
powdered grades of mannitol are used
for wet granulation, granular grades are
used for dry-blended direct compression
tablet formulation [23].
As an active ingredient mannitol acts
as an osmotic diuretic agent and weak
renal vasodilator [24].
3.3 Maltitol
Maltitol is derived by hydrogenation
from the disaccharide maltose (Fig. 17)
obtained from starch saccharification.
A sweetness of up to 90% relative to
sucrose makes maltitol a sugar substi-
tute not requiring the addition of high
intensity sweeteners.
Crystalline maltitol exhibits a similar
subtle cooling effect and about the same
bulk density as table sugar. Food use of
maltitol extends from sugarless hard
Fig. 12: Sorbitol in polyether polyol production
Fig. 13: Dehydration of sorbitol to sorbitan and isosorbide
starch or sugar by hydrogenation, by fermentation or by natu-
ral product extraction.
Hydrogenation of fructose (Fig. 16) yields a 50/50 mixture of
sorbitol and mannitol. Slightly alkaline hydrogenation condi-
tions improve the mannitol yield. Fructose syrups of 90–95%
are obtained by chromatographic enrichment of high fructose
corn syrups or invert sugar [19].
candies, chewing gum, chocolates, and baked goods to ice
cream. e low caloric value of 2.1 kcal/g however, is combined
with the highest glycemic index of all sugar alcohols, i.e. 35%
relative to glucose but still only half of that of sucrose. e
laxative effect of maltitol requires labelling in some countries.
As maltitol is not metabolized by oral bacteria, it is accorded a
“tooth-friendly” health claim [25].
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As an excipient in pharmaceutical drugs,
maltitol syrup is used as low calorie
sweetening agent, e.g. in cough syrup.
e low tendency of crystallization and
the hygroscopic properties of maltitol
makes it a humectant and emollient, e.g.
in skin moisturizer. It also is used as a
plasticiser in gelatine capsules [26].
3.4 Isomalt [27]
Isomalt is produced from sugar by fer-
mentation of sucrose to isomaltulose
and further hydrogenation of the reduc-
ing fructose moiety to an equimolar
mixture of 1,6-glucopyranosyl--sorbi-
tol and 1,1-glucopyranosyl--mannitol
that crystallizes with about 5% of crys-
tal water content (Fig. 18).
Isomalt exhibits about half the sweet-
ness of sucrose and is often combined
with sucralose to provide a 1:1 sugar
substitute.
A minimal cooling effect and the low
food energy content of 2.0 kcal/g at
a low glycemic index of 9% relative to
glucose has stimulated its use mainly
in sugar free, calorie reduced and non-
cariogenic confectionary products also
suited for diabetics.
As a sugar alcohol isomalt can cause
gastric distress including flatulence and
diarrhoea. erefore, its use is advised
not to exceed a daily intake of 50 g for
adults and 25 g for children.
3.5 Lactitol [28]
Lactitol is a sugar alcohol obtained by
the hydrogenation of lactose (Fig. 19).
This disaccharide consists of the two
sugar moieties galactose and glucose,
and is obtained by ethanol precipitation
from whey. In lactitol the glucose unit
is reduced to a sorbitol unit resulting
in the structure of 4-O-b--Galactopy-
ranosyl-D-sorbitol.
Lactitol crystallizes in the form of lac-
titol mono-, di- and trihydrate of which
the monohydrate and the a-anhydrous
form are of commercial interest. It is only
about 40% as sweet as sucrose. e low
caloric value of 2.0 kcal/g and the low
glycemic index of 4% relative to glucose
make it a bulk sweetener for low calorie
and dietetic foods such as sugar-free can-
dies, cookies, chocolate and ice cream.
Fig. 14: Sorbitan derived surfactants
Fig. 15: Isosorbide therephthalate in rigid PET structure
Fig. 16: Hydrogenation of fructose to mannitol
Fig. 17: Hydrogenation of maltose to maltitol
Fig. 18: Hydrogenation of isomaltulose to isomalt
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Similar to sucrose in terms of freezing point depressing effect,
hygroscopicity and solubility, lactitol is used as a sugar replacer
in frozen products.
e use as a prebiotic for colon health is related to the laxa-
tive effect as the majority of ingested lactitol reaches the large
intestine thus becoming fermentable to intestinal bacteria.
Lactitol is used in pharmaceuticals and cosmetics products as
an excipient, a laxative to treat constipation and in toothpaste.
3.6 Xylitol [29]
Xylitol is produced from xylan, a hemicellulose, extracted from
hardwoods or corncobs, hydrolyzed into xylose, a 5-carbon
sugar, which is catalytically hydrogenated into xylitol (Fig. 20).
Xylitol is roughly as sweet as sucrose and exhibits a strong
cooling effect. e low energy content of 2.4 kcal/g and the
very low glycemic response factor of only 3% relative to glu-
cose makes it a sweetener mainly for medicines, chewing gum
and pastilles.
Xylitol-based products are allowed by the US Food and Drug
Administration (FDA) to make the medical claim that they
do not promote dental cavities. is “tooth friendly”-claim is
related to xylitol being non-fermentable for oral bacteria.
As a result of the low fermentability of xylitol also by intes-
Fig. 19: Hydrogenation of lactose to lactitol
Fig. 20: Hydrogenation of xylose to xylitol
tinal bacteria, it has a higher laxation
threshold and is more easily tolerated
than mannitol and sorbitol.
Xylitol is used in pharmaceutical appli-
cations as a non-cariogenic sweetening
agent in tablets, syrups and coatings.
3.7 Erythritol [30]
Erythritol is a 4-carbon sugar alcohol
obtained by yeast fermentation of glu-
cose or sucrose (Fig. 21).
A sweetness of 80% relative to sucrose
combined with the strongest cooling
effect known for commercial sugar alco-
hols (–43 cal/g) and the lowest food
energy value of 0.2 kcal/g without any
glycemic response makes erythritol
rather a non-caloric bulk sweetener, e.g.
in zero calorie soft drinks, not affecting
blood sugar levels at all.
e unique digestion pathway of absorb-
ing 90% of the erythritol into the blood
stream in the small intestine and excre-
tion via the urine only allows for 10%
to enter the large intestine and is also
much more difficult for intestinal bacte-
ria to digest. It therefore does not nor-
mally cause gastric or laxative effects.
Erythritol is difficult to metabolize also
for oral bacteria therefore allowing for
a non-cariogenic, tooth-friendly health
claim.
Fig. 21: Fermentation of glucose or sucrose to erythritol
As an excipient in pharmaceutical drugs erythritol combines
the advantages of sweetness and chemical stability with non-
hygroscopic and non-glycemic properties. However, there is a
strong propensity to crystallize.
4 Conclusion
In the short history of only 60 years of industrial polyols pro-
duction, sorbitol and the whole range of sugar alcohols have
enjoyed a fast developing world-wide demand driven by a wide
range of applications in the food, cosmetics, pharmaceutical,
chemical and technical industries.
e today commercially available polyols cover a wide range of
looked for application properties to provide bulk sweetness at
low calorific value combined with a cooling effect resulting in
a pleasant cool taste. Crunchiness, compressibility, solubility,
and hygroscopic properties providing humectancy, make them
a versatile and widely used ingredient in food products.
e combination of rather unique properties explain the inter-
est in polyols not only as low caloric sweeteners; the manifold
functionality of e.g. sorbitol beyond sweetness makes it a
bulking agent, humectant, binder, complexing agent, plasti-
cizer and chemical reactant. Sorbitol has become a commodity
product competing successfully with other bulk chemicals
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such as natural glycerine, propylene glycol (PG) and polyeth-
ylene glycol (PEG).
e carbohydrate origin at improved chemical stability makes
polyols and their derivatives valuable chemical building blocks
whenever “green chemistry” solutions are intended.
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Paper received on 19 March 2013
Authors’ addresses: Michael A. Radeloff, Thales-Consult,
Wielandstraße 11, 12159 Berlin, Germany; e-mail: michael.
radeloff@thales-consult.com
Roland H.F. Beck, Sensient Food Colors Germany, Geesthachter
Strasse 103, 21502 Geesthacht, Germany; e-mail: roland.
beck@sensient.com