Cellulose Ethers 1

Cellulose Ethers
Heiko Thielking, Wolff Cellulosics GmbH & Co. KG, Walsrode, Germany
Marc Schmidt, Wolff Cellulosics GmbH & Co. KG, Walsrode, Germany

1. Introduction . . . . . . . . . . . . . . . 1 4.2.2. Synthesis . . . . . . . . . . . . . . . . . . 10

2. Properties . . . . . . . . . . . . . . . . . 1 4.2.3. Processes . . . . . . . . . . . . . . . . . . 11
2.1. Swelling and Dissolving Behavior . 2 4.2.4. Characterization . . . . . . . . . . . . . 11
2.2. Solution State . . . . . . . . . . . . . . 2 4.3. Hydroxyethyl Cellulose (HEC) . . . 13
2.3. Thermally Induced Coagulation . . 4 4.3.1. Applications / Market . . . . . . . . . . 13
2.4. Degree of Substitution . . . . . . . . . 4 4.3.2. Synthesis . . . . . . . . . . . . . . . . . . 13
2.5. Molar Mass Distribution . . . . . . . 5 4.3.3. Processes . . . . . . . . . . . . . . . . . . 14
3. Production . . . . . . . . . . . . . . . . 5 4.3.4. Characterization . . . . . . . . . . . . . 14
4. Product Groups . . . . . . . . . . . . . 7 4.4. Hydroxypropyl Cellulose (HPC) . . 15
4.1. Carboxymethyl Cellulose (CMC) . . 7 4.4.1. Applications/Market . . . . . . . . . . . 15
4.1.1. Applications / Market . . . . . . . . . . 7 4.4.2. Synthesis . . . . . . . . . . . . . . . . . . 15
4.1.2. Synthesis . . . . . . . . . . . . . . . . . . 8 4.4.3. Processes . . . . . . . . . . . . . . . . . . 15
4.1.3. Processes . . . . . . . . . . . . . . . . . . 8 4.4.4. Characterization . . . . . . . . . . . . . 15
4.1.4. Characterization . . . . . . . . . . . . . 8 5. Uses . . . . . . . . . . . . . . . . . . . . . 16
4.2. Methyl and Hydroxyalkyl Methyl 6. Economic Aspects . . . . . . . . . . . . 16
Celluloses . . . . . . . . . . . . . . . . . 10 7. Toxicology and Occupational Health 16
4.2.1. Applications / Market . . . . . . . . . . 10 8. References . . . . . . . . . . . . . . . . . 17

1. Introduction carried out by both industry and academia. Re-

Cellulose ethers are nontoxic, usually water-
soluble, white to yellowish powders or gran-
ules. There are some cellulose ethers that are
not soluble in water, but their share of sales is
insignificant as compared with the water-soluble
substances. Cellulose ethers are produced by a
polymer-analogous reaction of cellulose with
low-molecular alkoxylating agents, which can
support further functional groups.
The manufacture of cellulose ethers was first
published in an article by W. Suida [1] in 1905
and the first patents [2] relating to their indus-
trial production were issued as early as 1918.
In the decade between 1920 and 1930 carboxy-
methyl cellulose was the first cellulose ether to
gain economic significance, followed by methyl
celluloses and hydroxyethyl cellulose some ten
years later. These three product categories still
dominate the market today.
During the time cellulose ethers have been
used, continuous intensive research focusing on
production processes and applications has been
search was and is imperative to enable this group
of substances to be utilized in ever new applica-
tions. Despite major progress in the areas of re-
gioselective synthesis and analytics over recent
years, the potential of these substances has by
no means been fully exploited [3, 4].
Cellulose ethers can be sorted by their eco-
nomic significance. The most important prod-
ucts in terms of sales are carboxymethyl-
celluloses (approx. 230 000 tons per annum),
methyl- and hydroxyalkylmethylcelluloses (ap-
prox. 120 000 t/a), hydroxyethylcelluloses (ap-
prox. 60 000 t/a) and hydroxypropylcellulose
(less than 10 000 t/a). The demand is served by a
small number of manufacturers, which employ
proprietory processes and have developed their
own areas of expertise.
2. Properties
Cellulose ethers are nontoxic, usually water-
soluble, white to yellowish powders or granules.

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a05 461.pub2
2 Cellulose Ethers
There are some cellulose ethers, that are not sol-
uble in water, but their share of sales is insignif-
icant as compared with the water-soluble sub-
stances.
The bulk density of cellulose ethers is bet-
ween 300 and 600 g/L. They are lightfast and
their storage life is claimed by the suppliers to be
between 18 and 36 months. Cellulose ethers turn
brown at elevated temperatures (around 200 ◦ C)
and show signs of decomposition above 250 ◦ C.
Their biodegradability can be influenced by the
degree of substitution.
Cellulose ethers are capable of swelling or
are colloidally soluble; they increase the viscos-
ity of the solvent and develop a specific rheolog-
ical profile. Depending on the substitution, cel-
lulose ethers in solution are surface-active (sur-
face tension: water 72 mN/m, carboxymethyl
cellulose 70 mN/m, hydroxyethyl cellulose 63
mN/m, methyl cellulose 54 mN/m). The non-
ionic derivatives are film-forming substances,
resulting in transparent films with a high elastic-
ity. Solutions and films obtained from cellulose
ethers are compatible with other hydrocolloids.
In many applications, however, where cer-
tain properties of an initially dry mixture such as
dissolving and solvent binding behavior (water
retention) are required, cellulose ethers are not
used in ready-made solutions, but are blended
with other solids,.
These three characteristics – dissolving be-
havior, the resultant solution structure, and the
cellulose ether’s capability of binding solvents –
depend on molecular characteristics such as the
type, number and distribution of the substituent
and the molar mass distribution.
In technical specifications generally only the
degree of purity, the viscosity in aqueous solu-
tion and in some cases the degree of substitution
are stated.
2.1. Swelling and Dissolving Behavior
The different swelling and dissolving behav-
ior of the various cellulose ethers originates
from the interplay of the hydrogen bonds bet-
ween free OH groups on the one hand and hy-
drophilic and hydrophobic substituent groups on
the other. This interplay can be imagined as be-
ing the gradual introduction of hydrophobic sub-
stituents into native cellulose. Starting from a
crystal structure based on hydrogen bridges, the
partial imperfection of this structure caused by
substituents results in free hydroxyl functions,
hence first the substance becomes soluble in al-
kalies and subsequently in water. Further ether-
ification with hydrophobic substituents results
in solubility in organic solvents and ultimately
thermoplasticity (intrinsic solubility).
Alongside the hydrophilic-hydrophobic in-
teraction which culminates in “thermodynamic
solubility”, the particle-size distribution has a
crucial impact on the obtainable state of solution.
Particle size determines the kinetics of the disso-
lution process. If the particles are too large, they
may not dissolve fast enough; they will swell
and release some of their outer layer into the so-
lution; due to the rising viscosity the mobility
within the solution will decrease, leaving undis-
solved particle residues which will no longer dis-
solve in a reasonable time. Particles, that are too
small, on the other hand, may cause formation
of lumps during the dissolving process. Again
this will ultimately result in undissolved parti-
cle residues preventing formation of a homoge-
neous solution.
To counteract these problems, most suppliers
issue recommendations as to which particle size
is best for a particular application. Some suppli-
ers also offer specially treated products for en-
hanced dispersibility. These are mostly powder
grades, whose initial dissolving rate is greatly
reduced (“delayed or retarded solubility”) to en-
sure that the substance is homogeneously dis-
tributed in the solvent before starting to dissolve.
This delay can be achieved, for instance, by a re-
versible cross-linkage with glyoxal. The rate of
dissolution is thus pH-dependent.
2.2. Solution State
The state of solution obtained, i.e., the sum of the
interaction between the cellulose ether and the
solvent and the intramolecular and intermolecu-
lar interaction of the cellulose ether molecules,
determines the rheological profile of a solution
or of an end product.
The standard rheological models of polymer
chains dissolved in coil formation can be used
to describe the characteristics of cellulose ether
solutions, depending on the intrinsic viscosity

(also referred to as Staudinger index) and con-
centration. All known polymeric solution states
from the diluted particle solution to the con-
centrated network solution [5] can thus be de-
scribed. However, on account of their inclina-
tion to form aggregates, cellulose ethers often
set scientists impossible tasks to solve.
The viscosity of a cellulose ether solution is
generally stated as a characteristic feature. Mea-
sured in a 2 wt% aqueous solution, it is some-
times included in the product grade designa-
tion for orientation purposes. At first glance this
seems to be useful, because many application-
related properties are dependent on the same mo-
lecular parameters as viscosity. On closer, more
discriminating examination, however, this turns
out to be misleading, first because the dissolving
and measuring methods differ from one supplier
to another, which can result in a similar product
having twice the viscosity, and second because
– although giving a rough guide – the viscos-
ity does not describe the solution structure and
seldom the product’s behavior in the final appli-
cation system.
In the range relevant to the applications the
viscosity of cellulose ether solutions rises dis-
proportionately with increasing concentration
and intrinsic viscosity:
viscositysolution ∝ viscositysolvent •
3.4
(concentration • intrinsic viscosity) a stituent group with the lowest molar mass is the
(0.5< a < 1.0; a: exponent of the Mark-
Houwink equation)
Most solutions show a pseudoplastic behav-
ior, which is very important in practical terms.
Many cellulose ether solutions manifest time-
dependent rheological functions, so the mea-
surements depend on how the sample has been
pretreated. The elasticity of the solutions also
increases with rising concentration and intrinsic
viscosity, but the exponents are different from
those of the viscosity function; therefore the cel-
lulose ether selected can modify the ratio of
viscosity to elasticity within certain limits [6].
Some application systems exhibit a solid-like
behavior at low shear stress and viscous flow
only starts at stress levels above the so-called
yield stress (plastic flow behavior).
The intrinsic viscosity describes the volume
“filled” by the free molecule. The intrinsic vis-
cosity is often used as a measure of the molar
Cellulose Ethers 3
mass or chain length; the correlation is shown by
the Mark-Houwink equation. When the intrinsic
viscosity is gauged, not only the molar mass is
determined but also the quality or performance
of the solvent. Therefore effects attributable to
pH, temperature and low-molecular salts, which
have a substantial impact on the solution struc-
ture, are also part of the analysis. Many cellu-
lose ethers can be salted out by “removing” the
hydration shell of the molecules. With the ionic
products, polyelectrolytic effects such as “repul-
sion” or “cross-linking” due to the charging of
the macromolecules among themselves or with
the charges of salts present in the solution also
need to be observed.
The maximum possible thickening effect is
predetermined by the used cellulose. The ac-
tual viscosity achieved by a cellulose ether de-
pends on how well chain scissions can be pre-
vented during the production process and on the
type and quantity of substituents introduced into
the cellulose molecule. Each substituent repre-
sents an increase in molar mass without an in-
crease in the chain length. This reduces the thick-
ening effect. The substituents are, of course,
indispensable for solubility and other proper-
ties; however, derivatives which predominantly
carry substituents with a low molar mass and
where the degree of substitution is not too high
are particularly effective thickeners. The sub-
methyl group which simultaneously cancels out
the intermolecular hydrogen bonds very effec-
tively. As pure methyl cellulose manifests a spe-
cific temperature-dependent dissolving behav-
ior, which restricts its universal use, mixed cel-
lulose ethers with a low degree of substitution
with hydroxyethyl or hydroxypropyl groups are
generally used as high-viscosity thickeners, for
instance in the construction sector.
The amount of cellulose ether used or its con-
centration in an aqueous solution has a simi-
larly great effect as that of the chain length.
When used as a thickener, the concentration
range employed is usually in the range of a mod-
erately concentrated network solution in which
the polymer chains are not isolated but looped,
forming a temporary physical suspension net-
work.
The temperature dependence (below the floc-
culation point) of the flow behavior of aqueous
cellulose ether solutions follows the principle
4 Cellulose Ethers
of temperature-time superposition. At a higher
temperature all the molecules move faster. If a
flow curve (shear stress as a function of the shear
rate) is plotted at a reference temperature, the
flow curve determined at a higher temperature
follows the same shear stress path, except that it
is merely shifted to higher shear rates. Accord-
ingly, at the higher temperature the viscosity val-
ues are on a lower level.
Changes in flow behavior are thus predeter-
minable (as long as there is sufficient distance
from the flocculation point). Therefore, when us-
ing the cellulose ether as a thickener in aqueous
systems, the rheological behavior can be very
reliably estimated above and below the refer-
ence temperature, if the flow activation energy
is known. In the case of many cellulose ethers
in aqueous solution the flow activation energy is
in the proximity of 40 kJ/mol. Additional sub-
stances dissolved in the water may cause a shift
in this value, but there is no fundamental change
in the correlations.
2.3. Thermally Induced Coagulation
The solubility of cellulose ethers with hydropho-
bic substituents like methoxy groups decreases
as the temperature rises, i.e., the performance
of the solvent deteriorates. Cellulose ether dis-
solved in a cold solution can be made to co-
agulate by heating the solution. The process is
reversible: when the solution cools down, the
cellulose ether dissolves again. Depending on
the selected type and degree of substitution, the
flocculation point of industrial used products is
varied between 30 and 100 ◦ C.
This is an important characteristic for indus-
trial production of cellulose ethers because in
this way byproducts and salts can be washed out
with hot water instead of with mixtures of water
and alcohol.
To assess the flocculation point with mixed
substituent groups, suitable flocculation dia-
grams have been published [7].
2.4. Degree of Substitution
The type of substituent and the degree of substi-
tution determine most of the properties of a cel-
lulose ether. With substituent groups where no
secondary substitution is possible (methyl, car-
boxymethyl), the molar substitution (MS), i.e.,
the absolute number of substituents per anhy-
droglucose unit, is identical to the degree of sub-
stitution (DS), i.e., the number of substituents
directly linked to the anhydroglucose unit. In
the case of substituents containing hydroxyl
groups (hydroxyethyl, hydroxypropyl), for ex-
ample, further (secondary) reactions with the
substituent can occur, i.e., there is no decrease in
the number of reactive centers. With these prod-
ucts a distinction has to be made between MS
and DS. Comparing MS and DS shows the pro-
portion of side-chain substitution. On account of
the simpler analytics involved, frequently only
the MS is stated.
To examine the characteristic features more
precisely, it is necessary to analyze the sub-
stituent distribution. Primary substitution (i.e.,
prior to any secondary reactions with the sub-
stituent) already involves three kinds of distri-
bution:
• Substituent distribution within an anhy-
droglucose unit: depending on the reagent, the
distribution can be between C-2, C-3, and C-6.
This distribution can be analyzed by means of
nuclear resonance spectroscopy or hydrolysis
and subsequent chromatography [8].
• Substituent distribution along the backbone
chain: in contrast to the random distribution
normally found, a strictly uniform substituent
sequence along the chain or a block structure
formation are conceivable as theoretical bor-
derline cases, which show up the different ef-
fects on solubility and therefore on the prop-
erties in general. To gain an impression of the
distribution along the chain, various break-
down methods and subsequent liquid chro-
matography or derivatization and gas chro-
matography coupled with mass spectroscopy
are used to obtain the proportions of non-,
mono-, di- and trisubstituted anhydroglucose
units. To assess the distribution of these units
along the chain, the results of analysis of frag-
ments of various lengths can be compared.
Appropriate methods have so far only been
developed for particular derivatives and only
few research scientists have a good command
of them [9, 10].
• Substituent distribution between the individ-
ual chains: the substituent density can also

vary between the individual chains of the cel-
lulose ether, one known example being the
nonsubstituted cellulose fibers in otherwise
clear-soluble products. With ionic products
the interchain distribution can be detected
by polarographic analysis and an appropri-
ate method for other derivatives is chromatog-
raphy after specifically marking the free hy-
droxyl groups. The problem with both meth-
ods is that the molar mass distribution has to
be known in order to carry out the assessment
[11].
In the case of derivatives where a reaction
with the substituent is possible, the potential
number of different anhydroglucose units and
their distribution increases randomly, and the
structure becomes enormously complex. At the
same time, however, the possibilities for adapt-
ing the hydrophilic-hydrophobic interaction to
suit individual applications increase as well.
2.5. Molar Mass Distribution
Knowing the molar mass or the molar mass dis-
tribution makes it possible in theory to access
various material functions. An absolute deter-
mination of these variables has so far only been
achieved in isolated cases and with an enor-
mous research input. Due to the “poor solubility”
and the propensity of most derivatives toward
association, producing time-stable molecularly
disperse solutions is only rarely possible. Fre-
quently it is a mixture of molecules, associates
and aggregates that is analyzed, and the results
are often impossible to interpret reliably.
It is precisely because of this complexity that
so many attempts to make a breakthrough have
been launched in the past, starting with “batch
methods” such as static and dynamic light scat-
tering in many different solvents, and “classify-
ing” methods such as ultracentrifugation, size-
exclusion chromatography and flow-field-flow
fractionation, and also combined methods in-
volving chromatography and various detection
systems. All these approaches have in common
that, although they give an interesting insight
into the solution structure, the results often de-
pend on how the samples have been prepared and
how they are influenced by the measuring pro-
cedure itself. Taking the measuring conditions
Cellulose Ethers 5
into account, some vital assertions can be made
relating to existing systems. However, only in
rare cases do the results stand up to compari-
son (between various methods) in respect of an
“absolute” molar mass distribution.
3. Production
Cellulose consists of chains of anhydroglucose
units (AGUs) linked together glycosidically (β-
1-4-bonds) (→ Cellulose). Accordingly, each
AGU still has three free hydroxyl groups which
vary in their reactivity and which can be con-
verted to ether groups in polymer-analogous re-
actions.
The free hydroxyl groups form intermolecu-
lar and intramolecular hydrogen bonds, so be-
fore the cellulose can be etherified it needs to
be ‘activated’. For this purpose the cellulose
is chemically converted, usually with sodium
hydroxide solution (caustic soda), in order to
open up its natural structure and to obtain a suf-
ficiently swollen material that is accessible to
further reagents. The outcome is known as al-
kali cellulose or soda cellulose. The degree of
swelling is controlled by the ratio of sodium hy-
droxide solution to cellulose and by the method
of adding suspending agents or swelling agents.
A minimum quantity of alkali (approx. 0.8 mol
per mole of AGU) is required to swell the cellu-
lose and for the reagents. During this activation
process several properties of the end product are
predetermined, because the degree of swelling
and the uniformness of the activation influence
the distribution of the substituents introduced in
the second stage of cellulose ether production.
After the cellulose has been activated, the
etherifying reagent is added. In principle, any
etherification reaction known in the context of
low-molecular alcohols could be applied, many
of which have been studied [3]. Two basic types
have become established in the industrial pro-
duction of cellulose ethers – reactions where
sodium hydroxide solution is consumed (e.g.,
Williamson ether synthesis) and reactions where
sodium hydroxide only acts as a catalyst (e.g.,
alkoxylation). The supernatant caustic solution
is neutralized after the reaction.
The kind of cellulose and its quality are cru-
cial with regard to the ultimate properties of the
cellulose ether. Therefore, many different types
6 Cellulose Ethers
of cellulose obtained from wood pulp or cot-
ton linters are used. The type of cellulose used
determines, among others, the maximum chain
length, hence the viscosity yield of the final cel-
lulose ether. The chain length is reduced on ac-
count of the chemical and thermal stresses im-
posed during the process. The incidence of chain
scissions is inherent in the production process
but can be selectively increased. Oxidative, acid
and radiation-induced decomposition are some
of the known degradation processes which, de-
pending on the product category, are used at var-
ious points in the process to obtain a desired low
viscosity.
Processes. The processes depend on the
synthesis-related reaction stages which can take
place in one set of equipment or in several sets
arranged in sequence.
A distinction is made between reactions at
ambient pressure and reactions carried out at up
to 30 bar, depending on the different reagents
and on the required weight percentage of cellu-
lose or cellulose ether in the reaction medium
(mass fraction). Heterogeneous syntheses are
used for industrial-scale production, whereas
homogeneous syntheses are so far only found
in research. Heterogeneous systems are clas-
sified by mass fraction into suspension pro-
cesses (mass fraction below 10 wt%) and slurry
processes (mass fraction approx. 10 – 50 wt%).
There is also the option of a gas-phase or vapor-
phase process, that works without an inert liq-
uid. The process technology and engineering is
adapted to meet the requirements of the mass
fraction involved.
The cellulose is usually supplied as rolls of
cellulose webs or as cellulose sheets. In the early
days of cellulose ether production, the cellu-
lose was treated in an alkali bath (approx. 15
– 20 wt% caustic soda) with the disadvantage
that the cellulose had not been ground and was
therefore not fully accessible to the activating
agent. Consequently, the activation process took
4 h and the ripening time 8 h or more [13]. Dur-
ing the ripening process the alkali cellulose was
kept in intermediate tanks where the reaction
was allowed to complete at a specific temper-
ature. Prior to the ripening stage any excess ac-
tivating agent was pressed out and the alkali cel-
lulose was then shredded. Storing it in ripening
tanks made handling more difficult and reduced
its processability.
To make the cellulose more accessible to the
chemicals involved, in modern processes the cel-
lulose is generally ground or milled before the
activating and reaction stages. The cellulose is
then alkalized with highly concentrated (approx.
30 – 70 wt%) aqueous caustic soda solution. Al-
kalization usually takes place in mixers or stirred
reaction vessels, depending on the mass fraction
and the reaction system. The mass fraction can
be selected to influence the water balance which
affects side reactions or reagent yield and also
the quality of the cellulose ethers. The way the
chemical reaction is engineered during the alka-
lization stage also has a significant effect on the
quality of the cellulose ethers (see above).
The reaction can be carried out either batch-
wise, semibatchwise (fed batch) or continu-
ously, and the reaction temperatures vary from
room temperature up to 110 ◦ C, depending on
the type of etherification. Here again, mixers
and stirred vessels are the established equip-
ment. There are some isolated patents describing
continuous processes in different equipment set-
ups [14 – 16]. The starting materials are fed as
solids or liquids under pressure. In some older
processes for the production of methyl or hy-
droxyalkylmethyl celluloses gaseous reagents
are used.
The equipment assembled downstream of
the reaction depends on the required degree
of purity. In general a distinction is made bet-
ween technical and nontechnical cellulose ethers
which differ in their content of byproducts and
neutralization products – predominantly salts.
Depending on the washing agents and the type of
wash (displacement or dilution-type wash) the
equipment used for solid-liquid separation in-
cludes suction filters, belt filters, drum filters,
centrifuges and decanters, operating either con-
tinuously or batchwise. The washing processes
are carried out in aqueous or alcoholic media,
depending on the product group.
If the product is still wet with solvent after the
washing sequence, the inert dissolving or wash-
ing agents can be recovered by displacing them
with water prior to the drying stage. Suitable
equipment for this are, for example, continuous
mixers. Auxiliary facilities are used for regen-
erating the reagents and washing media and for
extracting byproducts.

At the end of the process line the products are
converted in forming stages from their fibrous
form into the required supply form, usually pow-
der grades with a defined particle size distri-
bution and containing small amounts of resid-
ual moisture (in most cases < 10 wt%). Various
drying and comminuting equipment is used in a
number of different combinations. This process
step is also utilized for modifying the cellulose
ethers so that they offer optimal properties for
the individual fields of application. The parti-
cle size distribution ranges from granular grades
with an average grain diameter of approx. 0.5
mm to very fine powders where the percentage
of particles with a diameter of less than 63 µm
is higher than 50 wt%.
4. Product Groups
4.1. Carboxymethyl Cellulose (CMC)
In terms of sales volume carboxymethyl cellu-
loses are the largest product group. They are
available in various levels of purity from com-
pletely “unpurified” to “highly purified” for
food-grade applications. The CMC group also
includes mixed ethers with hydroxyalkyl sub-
stituents, that have a predominantly ionic char-
acter. The structure of CMC is shown in Figure 1.
Figure 1. Structure of CMC
4.1.1. Applications / Market
The market can be divided into two segments:
one for “purified” and another for “unpurified”
CMC. However, the terms “purified” and “un-
purified” are subject to regional and supplier-
Cellulose Ethers 7
specific differences in definition. Products with
an active content of 55 – 85 % are considered
to be “unpurified”; 85 – 95 %: “semi-purified”;
around 98 %: “purified”; and products with an
active content greater than 99.5 % are classed as
“highly purified” (high-purity grades).
Annual sales worldwide amount to approx.
230 000 t, of which purified CMC accounts for
130 000 t and unpurified CMC totals 100 000 t.
It is difficult to accurately apportion figures to
the two segments, not only because of varying
definitions but also due to the fact that in some
applications both purified and unpurified grades
of CMC can be used, and many suppliers have
both purified and unpurified products in their
portfolios.
CMC can be produced with less technologi-
cal input than the other cellulose ethers, which
explains why a comparatively large number of
manufacturers (more than 20) exists. The lead-
ing producer is CP Kelko with a market share
of around 33 %. The largest regional market and
the region with the largest production capacity is
currently Europe, which still accounts for some
60 % of global capacity.
The initial application fields of CMC were
detergents, where it acts as a soil carrier, and
in deep-well drilling for oil and water, where it
is used as a flotation aid in drilling mud. Un-
purified grades were and in some cases still are
used in these applications. Purified products are
used in surface coatings and various other tech-
nical areas such as in the paper industry for
coatings and pulp sizing to improve fiber reten-
tion, filler/pigment/dye yield as well as strength.
CMC also improves the printability and smooth-
ness of paper. Together with gelatin CMC is used
as a coacervate to encapsulate ink in the produc-
tion of noncarbon copy papers. Users of high-
purity grades include the cosmetics and phar-
maceutical industries, where CMC is used for
instance as a fat-free ointment base or as a tablet
disintegrant. In food and pet food production
CMC’s simplest function is to improve consis-
tency and to provide a low-calorie replacement
for starch and proteins, or to control more com-
plex functions such as the freeze-thaw stability
of deep-frozen products or the creaminess of ice
cream.
8 Cellulose Ethers
4.1.2. Synthesis
CMC is produced in a Williamson ether synthe-
sis from alkali cellulose with sodium chloroace-
tate or with chloroacetic acid itself, which reacts
in-situ with caustic soda to form the salt. The
process takes place in an aqueous or aqueous-
alcoholic medium (slurry). The alcohols used
are ethanol, isopropanol, tert-butanol and mix-
tures thereof.
Cell−OH·NaOH+ClCH2 COONa→
Cell−O−CH2 COONa+NaCl+H2 O
Alkalyzation is carried out at room temper-
ature; the reaction takes place between 50 ◦ C
and the boiling point of the slurry medium un-
der appropriate system pressure. The reaction
is exothermic. With an activation energy of
87.9 kJ/mol it is highly temperature-dependent.
The yield from this reaction in relation to
chloroacetic acid is between 65 % and 80 %. Hy-
drolysis of chloroacetic acid occurs as a side re-
action, forming glycolate. Commercial CMCs
are produced with a degree of substitution bet-
ween 0.2 and 1.5. Carboxymethylation takes
place with a slight preference toward C2- fol-
lowed by C6- and C3-substitution of the anhy-
droglucose unit [17].
4.1.3. Processes
In the early days of CMC production the cel-
lulose was activated in alkaline steeping tanks
[18]. After the excess caustic soda solution had
been pressed out and the alkali cellulose had
been shredded to fibers, the reaction was carried
out with the addition of sodium chloroacetate in
a kneader, where temperatures reached 30-35◦ C.
The reaction was completed in a tumbling drum
at 50 ◦ C. The material was then washed with a
mixture of methanol and water, filtered, ground
and finally dried.
The first continuous process was used by
Wyandotte Chem. Corp. (1947), but there was no
washing stage, so it was only suitable for unpuri-
fied CMC [19]. Sodium hydroxide solution and
monochloroacetic acid were added to the ground
cellulose in a rotating drum. After a dwell time
of 3 h the product was allowed to “ripen” for 10
h in drums.
In contemporary CMC production processes
the ground cellulose is processed batchwise ei-
ther as a suspension in the case of a low mass
fraction of cellulose or, if the mass fraction is
high, in mixers in the presence of “inert” me-
dia (see Fig. 2). Both processes use one or
more short-chain alcohol(s) as a mass-transfer
and heat-exchanging medium or as a suspending
agent. For processes with a high mass fraction
ethanol is usually employed a slurry medium,
whereas isopropanol is used in suspension-type
processes [20, 21]. By placing several sets of the
same kind of equipment in parallel or in series
it is possible to implement a quasi-continuous
operation in the activation and reaction stages.
The starting materials and suspension or
slurry media are either solid or liquid at normal
room and reaction temperatures. Activation and
reaction can therefore be carried out at ambient
pressure.
Depending on the required product purity, the
product is washed with alcohol-water mixtures,
preferably with the same alcohol used in the re-
action. Washing with water is not possible be-
cause of the water-solubility of the products. To
meet product purity requirements, it is necessary
to remove the alcohols from the product after the
washing stage and prior to the grinding and dry-
ing processes.
Suspension agents and washing liquids are
collected and reprocessed either by distillation
and extraction or membrane processes.
4.1.4. Characterization
Carboxymethyl cellulose becomes water-
swellable or alkali-soluble even at a low degree
of substitution. The water-solubility of industri-
ally produced CMC begins at a DS of approx.
0.6. The solubility increases up to a rather the-
oretical DS value of 3.0. Research work has
shown that products with a lower degree of
substitution (DS < 0.6) can manifest good sol-
ubility, the reason being different substituent
distribution along the backbone [22].
Aqueous carboxymethyl cellulose solutions
have very complex solution structures, because
boundary conditions such as pH or salts simulta-
neously affect various characteristics. The solu-
tion state achieved depends, as with other cellu-
lose ethers, on the nature of the dissolution pro-

Figure 2. Reaction mixer processes for purified CMC production
a) Cellulose shredding; b) Cellulose buffer; c) Slurry medium dosing vessel; d) Caustic soda dosing vessel; e) Chloroacetic
acid dosing vessel; f) Reaction mixer; g) Washing vessel; h) Filtration equipment; i) Dryer; j) Comminuting; k) Screening
equipment; l) Slurry medium recycling
cess and the performance of the solvent. The pa-
rameter “solvent performance” covers all ther-
modynamic effects of protons, salts and other
low-molecular substances on the interaction bet-
ween the solvent and the macromolecule.
In addition CMC is a weak carboxylic acid.
The proton concentration in the solution not only
affects the solvent’s performance but simulta-
neously alters the number of free carboxylate
groups. CMC’s equivalence point is at a pH of
8.25; its pK a value is between 4 and 5. In its acid
form CMC is insoluble in water. Depending on
the degree of substitution CMC can be precip-
itated from the solution at low pH values. De-
protonation increases with rising pH values and
the character of the polyelectrolyte becomes ap-
parent: The repulsion among the individual sub-
stituents becomes more distinct and the salt sen-
sitivity increases. When CMC comes into con-
tact with selected divalent or trivalent salts, this
leads to complexing and in some cases to in-
terlinking and precipitation of the CMC. With
divalent salts these effects depend largely on the
ratio of substituent to salt [23].
Cellulose Ethers 9
The many different possibilities of micro-
scopic interaction are also reflected in the macro-
scopic properties of CMC. From a rheological
point of view CMC solutions are inclined to
form superstructures. Viscosities of 2 wt% so-
lutions ranging from 3 mPa·s to 100 000 mPa·s
are available on the market. Most of the prod-
ucts exhibit pseudoplasticity, some of them a
thixotropic behavior. Depending on the selected
degree of substitution and the product group,
the solutions are either smooth-flowing or highly
gelatinous.
Commercial grades are not only categorized
according to their purity, their morphology and
their mean viscosity, but also according to their
degree of substitution. Water-soluble CMC com-
modities are available with a DS of around 0.7,
0.9 and 1.2. These three product groups do not
only differ in their DS, but also in their solution
structure, hence their rheological behavior.
10 Cellulose Ethers
4.2. Methyl and Hydroxyalkyl Methyl
Celluloses
Pure methyl cellulose (MC) and hydroxyalkyl
methyl celluloses (HAMC) are collectively
known as methyl cellulose. Pure methylcellu-
lose only accounts for a minor share of the
market. The mixed ethers hydroxyethyl methyl
cellulose (HEMC, see Fig. 3) and hydroxypro-
pyl methyl cellulose (HPMC) have established
themselves in particular for technical applica-
tions.
Figure 3. Structure of HEMC
4.2.1. Applications / Market
The market for methyl cellulose and hy-
droxyalkyl methyl celluloses was in the range
of 120 000 t in 2003, the market leader being
Dow Chemical Company, with Shin-Etsu Chem-
ical and Wolff Cellulosics having slightly lower
market shares. High-purity grades are marketed
for applications in the food, pharmaceutical and
cosmetics sectors and purified products are used
in building materials and industrial applications.
The building material segment is by far the
largest field of application.
The applications and therefore also the types
of product used in the building materials sector
vary from region to region due to different con-
struction methods and traditions (→ Dry Mor-
tars). In the USA joint compounds account for
the largest segment; in Europe the main appli-
cations of MC and HAMC are plasters, renders,
and tile adhesives. Efficient modern application
methods would not be possible without the use
of methyl celluloses. Properties such as water re-
tention, open time, wet adhesion, initial thicken-
ing and setting behavior are regulated using only
low additive contents of between 0.01 and 2 wt%
(in relation to the building material system). Ac-
cordingly, the cellulose ether has to meet high
quality requirements.
In the life-science sectors only nonhy-
droxyalkylated methyl cellulose (modified veg-
etable gum) and hydroxypropyl methyl cellulose
(carbohydrate gum) are used. In the pharmaceu-
tical industry methyl celluloses are employed as
tablet base and in coatings of controlled-release
drugs. In the food and cosmetics industries it is
the thickening and emulsifying properties that
are exploited to give the products the desired
consistency and texture. The most noteworthy
industrial application is the use of highly methyl-
ated hydroxypropyl methyl cellulose as a protec-
tive colloid in the polymerization of vinyl chlo-
ride.
4.2.2. Synthesis
The synthesis of hydroxyalkyl methyl cellulose
is a combination of both principles of synthesis
in industrial cellulose ether production: methy-
lation is along the lines of Williamson ether syn-
thesis where a stoichiometric amount of NaOH
solution is consumed, whereas alkylation only
requires catalytic amounts of alkaline solution.
Pure MC is produced from alkali cellulose by
a reaction with gaseous or liquid methyl chlo-
ride. In side reactions the methyl chloride is hy-
drolyzed to form methanol, and subsequently the
methanol is etherified by methyl chloride, form-
ing dimethyl ether. The reactions take place bet-
ween 70 and 120 ◦ C. Methylation is an exother-
mic reaction, the activation energy being 80
kJ/mol.
Cell−OH·NaOH+ClCH3 →Cell−O−CH3 +NaCl+H2 O
The grades produced have a degree of substi-
tution of 1.7 and 2.3. In case of pure methylation
the substituent is found to prefer C2-, followed
by C6- and C3-positions of the anhydroglucose
unit [25, 26].
In the course of hydroxyalkyl methyl cel-
lulose production alkoxylation of the cellulose
takes place prior to or parallel to its methyla-
tion. As both the cellulose and the alkoxy groups
formed can be methylated and alkoxylated, the
outcome is a potentially indefinite number of

different products, allowing the range of proper-
ties to be tailored to the requirements of specific
applications.
4.2.3. Processes
The development of processes to produce methyl
cellulose and hydroxyalkyl methyl celluloses
began with methods at ambient pressure, i.e.
gas circulation processes, where the cellulose
is activated (for example by a steeping process),
shredded and subsequently brought into contact
with the reagents in a mixer. Nonreacted gaseous
feed materials and byproducts are continuously
extracted, the byproducts are condensed out and
the gas flow is returned to the reactor. The prod-
uct is then washed, filtered, compressed, ground
and dried.
The slurry process (see Fig. 4), operated
at pressures of up to 30 bar, is the process
in most widespread use today for producing
HAMC batchwise or semibatchwise in a mixer.
Processes patented in the 1950s suggest the
use of pressure-resistant reactors without any
additional inert slurry media [27]. More re-
cent patents propose adding inert slurry media,
mostly ethers [28]. The slurry medium acts as a
heat-transfer medium, which evaporates and is
condensed in a dome-shaped condenser.
The reagents are added to the ground cellu-
lose in any sequence, depending on the targeted
product characteristics. The slurry medium has
to be added prior to etherification on account
of the heat generated during the exothermic re-
actions. Once the reaction has been completed,
low-boiling slurry media are extracted by re-
ducing the pressure and are collected for reuse.
Byproducts are discharged. High-boiling slurry
media are separated during the washing stage
and subsequently reprocessed.
Suspension-type processes are mentioned in
several patents. Their advantages are their sim-
ple process engineering, whereas disadvantages
can be seen in the more complex preparation of
the suspension agent.
The flocculation point of MC and HAMC al-
lows the products to be washed with water above
this flocculation point. To do so, the contents of
the reactor are led into a stirred tank filled with
hot water or they are suspended in the reaction
mixer; the salts formed during the reaction are
Cellulose Ethers 11
dissolved and any nonreacted activation reagents
are neutralized with acid. The suspension is then
separated in a solid-liquid separating unit. Fur-
ther washing stages may be required, depending
on the product specifications, in order to comply
reliably with restrictions in content of byprod-
ucts.
Again depending on the type of product, the
HAMC is then conditioned for the grinding and
drying stage. Drying and grinding can be carried
out in succession or in combined milling and
drying units. The required fineness of grind, i.e.,
the particle size, which in some cases is less than
63 µm in more than 50 wt% of the product, can
often only be achieved in screening and sifting
stages, after which the coarse-grained material
is recycled.
4.2.4. Characterization
With a degree of substitution of around 1, methyl
celluloses exhibit good water solubility at room
temperature. The higher the degree of substitu-
tion, the better the solubility in water. However,
it decreases again with further methylation and
changes to solubility in organic solvents at a DS
of approx. 2.6, because the material becomes in-
creasingly hydrophobic.
Available on the market are pure methyl cel-
luloses with a degree of substitution between
1.7 and 2.3, hydroxyethyl methyl celluloses
with methylation levels between 1.3 and 2.0
and ethoxylation levels between 0.1 and 0.4,
and hydroxypropyl methyl celluloses with de-
grees of methylation between 1.3 and 2.1 and of
propoxylation between 0.1 and 1.0. The limits of
substitution are more or less predetermined by
the products’ flocculation point, because wash-
ing with water is less expensive than with alco-
hol.
The flocculation point, i.e., the gelation and
subsequent coagulation as the temperature rises,
is a characteristic found only in nonionic cellu-
lose ethers. By varying the methyl and/or alkyl
content of hydroxyalkyl methyl celluloses, it is
possible to modify the macromolecule’s affinity
to its water shell and therefore the flocculation
point: with increasing methyl substitution the
number of hydrophilic groups is reduced, and
the flocculation point drops. Accessibility to the
hydrophilic groups increases in proportion to the
12 Cellulose Ethers
Figure 4. Modern HAMC production process
a) Cellulose shredding; b) Cellulose buffer; c) Caustic soda dosing vessel; d) Alkoxylation agent dosing vessel; e) Methyl chlo-
ride dosing vessel; f) Reaction mixer; g) Washing vessel; h) Gas buffer; i) Filtration equipment; j) Conditioning equipment;
k) Comminuting; l) Stream dryer; m) Screening equipment; n) Slurry medium recycling
rise in hydroxyethylation, and the flocculation
point shifts to higher temperatures. (The intro-
duction of hydroxypropyl substituents results in
opposite characteristics where, depending on the
degree of substitution, the flocculation point ei-
ther rises or drops.) Especially for applications
where there is a high ambient temperature, e.g.
on building sites in the summer, a methyl cellu-
lose (MHEC or MHPC) with a sufficiently high
flocculation point should be used to eliminate
any undesired changes in characteristics.
The rheological properties of methyl cellu-
loses and hydroxyalkyl methyl celluloses vary
within a broad range, exhibiting some very dif-
ferent features, because there is a wide viscosity
range in the grade spectrum available and be-
cause the products can have very differing chem-
ical structures.
Products with a particularly low viscosity,
such as HPMC for tablet coatings with a typ-
ical viscosity of between 3 and 6 mPa·s at a
concentration of 2 wt% in water, still show a
purely Newtonian (ideal) flow behavior in aque-
ous solutions with a HPMC concentration of 10
– 20 wt% at room temperature, and the viscos-
ity of these solutions can be as high as 10 000
mPa·s. The Newtonian behavior is crucial for
spraying highly concentrated solutions and for
good leveling and film formation.
HEMC or HPMC grades with a higher vis-
cosity for use as thickeners, however, exhibit
a non-Newtonian flow behavior even with at
low concentrations. In building materials appli-
cations, such as tile adhesives, the high static
shear viscosity guarantees standing strength and
resistance to demixing as well as high water re-
tention, while the non-Newtonian properties en-
sure rapid and easy workability. The thickening
characteristics of nonionic cellulose ethers are
scarcely affected by the presence of dissolved
(even polyvalent) salts or by changes in the pH
value, so they are also ideal for use in cement-
based building materials in which, after water is
added, highly alkaline conditions prevail.
The most effective way to achieve good thick-
ening at a low shear rate is to use small input
quantities of high-viscosity grades. In these sys-
tems the viscosity soon drops considerably as the
shear rate increases. A high thickening effect at
high or at least at medium shear rates is desirable
for improved workability in certain high-quality
building material systems, and it can only be
obtained with higher levels of methyl cellulose,
which also provide additional benefits, such as

long open times and improved adhesion in the
case of tile adhesives.
4.3. Hydroxyethyl Cellulose (HEC) [29]
Hydroxyethyl celluloses are the third largest
product group in the marketplace. They are non-
ionic and soluble in both cold and hot water.
Their manufacture was first described in 1920
in a patent granted to Farbenfabriken Bayer. The
structure of HEC is shown in Figure 5.
Figure 5. Structure of HEC
4.3.1. Applications / Market
The hydroxyethyl cellulose market is served
mainly by Hercules Incorporated/Aqualon and
Dow Chemical Company. Annual sales are
around 60 000 t, most of which are used in the
construction industry, and specifically in sur-
face coatings. Hydroxyethyl cellulose is also
found in cosmetic applications where it com-
petes against HPMC derivatives. Other applica-
tions are in drilling fluids and as a protective
colloid in emulsion polymerization.
In the paint industry HEC is the cellulose
ether product group with the largest market
share. Although products based on HEMC,
HPMC or CMC have smaller shares, they are
firmly established in these applications for tech-
nical and cost-related reasons. Beside pure HEC
this product group also includes mixed cellu-
lose ethers similar to HEC: ethyl hydroxyethyl
cellulose (EHEC) and hydrophobically modified
(hm) variants of HEC. The additional hydropho-
bic properties are imparted to hm-HEC by minor
secondary substitution, for instance with long-
chain alkyl residues (C12 through C24 ) [30]. The
Cellulose Ethers 13
hydrophobically modified grades are, like purely
synthetic associative thickeners, capable of pro-
viding additional effects by interacting with par-
ticle surfaces, in particular those of the binder in
latex paints, and by forming micelles and mixed
micelles with other surfactants contained in the
paint. These options are exploited especially in
high-grade paint formulations in order to reduce
spattering when applying the paint with a roller,
and to obtain improved brush resistance and lev-
eling.
4.3.2. Synthesis
Hydroxyethyl cellulose is formed by reaction of
cellulose with ethylene oxide. This ethoxylation
only requires catalytic quantities of alkaline so-
lution.
Cell−OH+OH− →Cell−O− +H2 O
Cell−O− +CH2 CH2 O→Cell−O−CH2 CH2 −O−
Cell−O−CH2 CH2 −O− +H2 O
→Cell−O−CH2 CH2 −OH+OH−
Just as the cellulose alcoholate reacts with the
ethylene oxide, also the hydroxyl ions present
can react with the ethylene oxide or with the gly-
colates formed in the process. Large amounts of
alkali reduce the yield of the main reaction, but
to produce HEC a minimum quantity of caus-
tic soda solution is essential to break down the
cellulose.
Ethoxylation takes place in the presence of
an “inert” solvent (isopropanol, tert-butanol,
1,2-dimethoxyethane or acetone); it starts at a
very low temperature (≈ 30 ◦ C) and is highly
exothermic. HECs are produced with a molar
substitution of 1.5 and 3.5, these degrees be-
ing controlled via the quantity of ethylene oxide
added. The yield is between 40 and 75 % in rela-
tion to ethylene oxide. The reaction of ethylene
oxide takes place in the following order of pref-
erence (from high to low): alkoxy groups, then
C6 positions, then (followed by some distance)
C2 and C3 positions [31]. The relationship of the
reaction rates can be influenced by varying the
alkali concentration, e.g., by partial neutraliza-
tion [32]. After the reaction has taken place, the
alkali quantity added needs to be neutralized.
14 Cellulose Ethers

Figure 6. Process for the production of HEC/HPC with stirred tanks

a) Cellulose shredding; b) Cellulose buffer; c) Slurry medium dosing vessel; d) Caustic soda dosing vessel; e) Acid dosing
vessel; f) Alkoxylation agent dosing vessel; g) Stirred reaction tank; h) Washing vessel; i) Washing and filtration process;
j) Stream dryer; k) Comminuting; l) Screening equipment; m) Slurry medium recycling

4.3.3. Processes 4.3.4. Characterization

For the production of HEC, suspension pro-
cesses above ambient pressure have become the
established methods [33]. Stirred pressure ves-
sels are used for the reaction (see Fig. 6).
The ground cellulose is suspended in the sus-
pending medium and mixed with the alkalizing
agent. After alkalization, liquid ethylene oxide
is added to the suspension and allowed to react
for about 2 h.
Salts and byproducts have to be washed out
of the products. As with other cellulose ethers,
this involves appropriate equipment for washing
and solid-liquid separation either in series or in
a combined unit. As this cellulose ether does not
have a flocculation point, mixtures of water and
an organic solvent are used, followed by drying
and grinding.
Parallel to this, the suspension medium and
any extracting agents have to be regenerated and
recycled. Distillation is the method usually se-
lected for this.
Hydroxyethyl celluloses are available on the
market with viscosities between 10 mPa·s and
100 000 mPa·s and molar substitutions of 1.5
and 3.0 (up to 4.5 in the case of hydrophobi-
cally modified grades). They are water-soluble
and have no thermal flocculation point. Hydrox-
yethyl celluloses are also more difficult to salt
out than methylated derivatives and are not dis-
placed from water even by larger amounts of or-
ganic solvent. The degree of substitution varies
in the region of 1 in industrially produced grades,
i.e., higher hydroxyethylation leads chiefly to
secondary, tertiary, and quaternary substitution
of the hydroxyalkyl substituent (formation of
ethylene oxide side chains).
The rheological behavior of HECs is com-
parable with that of carboxymethyl celluloses.
By introducing a small number of hydrophobic
side chains, grades can be obtained, whose rhe-
ological profile in solution is highly modified,

particularly when mixed with surfactants. The
hydrophobic residues form part of the surfac-
tant micelles and this increases the viscosity, es-
pecially at elevated shear rates.
4.4. Hydroxypropyl Cellulose (HPC)
In relation to the quantities of cellulose ethers
used worldwide, hydroxypropyl celluloses are
the smallest product group. Their properties
range from simple swellability, through solu-
bility in cold water to enhanced thermoplas-
ticity, which enables them to be processed in
melt extruders. Hydroxypropyl cellulose was
first launched on the market in the USA at the
end of the 1960s. The structure of hydroxypro-
pyl cellulose is shown in Figure 7.
Figure 7. Structure of HPC
4.4.1. Applications/Market
The annual global market for hydroxypropyl cel-
lulose is far below 10 000 t. The main fields of
application are in the pharmaceutical and cos-
metics industries [34]. High-purity grades are
available for food and pharmaceutical applica-
tions, and purified grades are supplied to the cos-
metics industry and for technical applications.
Hydroxypropyl cellulose is supplied by
Hercules Incorporated/Aqualon, by Shin-Etsu
Chemical and by Nippon Soda.
4.4.2. Synthesis
The synthesis of hydroxypropyl cellulose does
not differ from that of hydroxyethyl cellulose.
Prior to the reaction with propylene oxide, the
Cellulose Ethers 15
cellulose is activated with caustic soda solution.
The reaction has a somewhat higher activation
energy and requires a higher reaction temper-
ature than that with ethylene oxide. The by-
products are propylene glycol and polypropyl-
ene glycols which, like the salts from the neu-
tralization stage, need to be removed in one or
several washing stage(s).
4.4.3. Processes
The production processes for HPC are largely
the same as for HEC. The reaction is gener-
ally carried out in a slurry. The slurry media de-
scribed in relevant literature are hexane, toluene,
tetrahydrofuran and dioxane, and also the com-
mon alcohols. Apart from the slurry process,
the gas-phase method — which produces high-
quality grades due to the high degree of sub-
stitution — is also applied. Since highly substi-
tuted HPC has a thermal flocculation point, how-
ever, washing can be carried out using hot water,
which is not possible with HEC [35].
4.4.4. Characterization
Highly substituted hydroxypropyl cellulose is
readily soluble in cold water and also soluble in
polar organic solvents. The HPCs available on
the market have a high molar substitution (3.0 –
4.5) and mean viscosities between 10 and 30 000
mPa·s. HPC solutions are generally smooth-
flowing and exhibit scarcely any tendency to-
ward thixotropic behavior. Gelation and coagu-
lation begins at relatively low temperatures (40
– 50 ◦ C). Hydroxypropyl cellulose is surface-
active and tends to foam. Highly concentrated
HPC solutions can develop liquid-crystalline
phases. With a sufficiently high degree of substi-
tution hydroxypropyl cellulose is thermoplastic
and can be processed at approx. 150 ◦ C. The ex-
truded moulded parts are water soluble yet, due
to their low propensity to absorb water, they are
not sticky even when the humidity is high.
HPC with a low molar substitution of bet-
ween 0.2 and 0.4, on the other hand, swells in
water, but is not water-soluble. These grades are
used as binders or disintegrants in the manufac-
ture of tablets.
16 Cellulose Ethers
5. Uses
Cellulose ethers are used in a wide variety of
fields ranging from oil drilling to industrial ap-
plications such as polymerization, from surface
coatings and construction materials to the health
care sector, cosmetics, food and pharmaceuti-
cals. Not all types of cellulose ethers are equally
suitable in all fields of application. Table 1 pro-
vides an overview of the great variety of appli-
cations and the appropriate types of cellulose
ether. A listing of this kind can only be incom-
plete, but indicates the versatility and above all
the adaptability of the products to the various
fields in which they are to perform.
In many cases the amount of cellulose ether
required is only between 0.02 and 2 %. This
small level is, however, crucial for properties
such as water-binding capacity, film formation
and thickening as well as for controlling other
rheological properties. Many modern products
and processing techniques would not be possi-
ble without the use of cellulose ethers.
Each field of application requires specific so-
lutions which in many cases involve modify-
ing the cellulose ether product. This means that,
once a suitable product category has been se-
lected, all the parameters relating to the appro-
priate type of substitution and viscosity range
have to be fine-tuned. Besides their chemical
structure, characteristics such as product purity
and forming, i.e., the physical state in which the
products are made available, play a substantial
part. Fine-tuning requires a great deal of experi-
ence in respect of the properties of these products
as well as with regard to the systems and meth-
ods of application. Most suppliers provide this
expertise and offer additional technical service.
6. Economic Aspects
In 2003 the sales volume of the cellulose ether
market worldwide was approximately $ 2 ×
109 . The largest market is Europe, followed by
the USA and Japan. Annual consumption is ca.
420 000 t.
Sorted in the order of their economic sig-
nificance (by sales volume), carboxymethyl-
celluloses rank first with approx. 230 000
t/a, while methyl- and hydroxyalkylmethyl-
celluloses are second with approx. 120 000 t/a,
followed by hydroxyethylcelluloses on third
place with approx. 60 000 t/a and last by hy-
droxypropylcellulose with less than 10 000 t/a.
Taking all market segments together, the cel-
lulose ether market has grown continuously in
recent years. However, there has been and still is
a noticeable shift among the individual markets.
As opposed to vigorous growth in the threshold
countries and moderate growth in Europe and
the USA, the Japanese market is dwindling.
The market is served overall by a small num-
ber of suppliers of cellulose derivatives. Most
of the manufacturers produce a variety of differ-
ent products for several market segments. The
carboxymethyl cellulose market is spearheaded
by CP Kelko, a company with a market share of
33 %. The remaining market is shared by 10 to 15
small to medium-size suppliers. The methyl and
hydroxyalkyl methyl cellulose market is served
by a few major producers [Dow Chemical Com-
pany, Wolff Cellulosics, and Shin-Etsu Chemi-
cal (incl. SE Tylose, the former cellulose ether
division of Clariant AG)] with a market share to-
taling 80 %. Hydroxyethyl cellulose is supplied
more or less exclusively by Hercules and Dow
Chemical Company, whereas HPC is mostly
supplied by Hercules and Shin-Etsu Chemical.
7. Toxicology and Occupational
Health
Toxicology. Cellulose ethers are generally
nontoxic. High-purity grades of most commer-
cial products are approved as food additives and
for use in cosmetic compositions.
Handling. Fine powders of cellulose ethers
form explosive dusts in air as do natural polysac-
charides or sawdust. Dry nonionic ethers un-
dergo electrostatic charging similar to that of
other organic polymers. When cellulose ethers
are stored and handled, the general precautions
concerning powdered organic polymers must be
observed. The flammability is similar to that of
cellulose. Spilling of solutions forms very slip-
pery films that are difficult to remove.
Ecology. The biodegradation of cellulose
ethers by cellulase-producing microorganisms
also occurs in wastewater and therefore prevents
the accumulation of cellulose ethers. Glucose,
glucose ethers, and ether oligomers result from
 Cellulose Ethers 17
Table 1. Major fields of application in which the individual product groups are used

Carboxymethyl Methyl cellulose, Hydroxyethyl Hydroxypropyl

cellulose hydroxyalkyl cellulose cellulose
methyl cellulose

Paper tile adhesives latex paints adhesives

Detergents plasters/renders adhesives ceramics
Drilling for oil and pharma/cosmetics building materials cosmetics
gas
Pharma joint compounds cosmetics encapsulation
Cosmetics wallpaper paste drilling for oil & gas food
Textile industry polymerization agriculture household goods
Food food paper printing inks
Coatings latex paints synthetic resins polymerization
Encapsulation cement extrusion textile industry films

enzymatic hydrolysis; they are further degraded
to carbon dioxide and water in slow bioreactions.
Biostable or toxic metabolites are not known.
Cellulose ethers have no fish toxicity and are
poor nutrients for most microorganisms. Nev-
ertheless, wastewater bacteria may adapt to en-
hanced cellulose ether degradation after some
exposure.
The suppliers provide Safety Data Sheets
containing detailed data with regard to handling
and the toxicological properties of the respective
products.
8. References
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18 Cellulose Ethers
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