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-

search was and is imperative to enable this group
Cellulose ethers are nontoxic, usually water- of substances to be utilized in ever new applica-
soluble, white to yellowish powders or gran- tions. Despite major progress in the areas of re-
ules. There are some cellulose ethers that are gioselective synthesis and analytics over recent
not soluble in water, but their share of sales is years, the potential of these substances has by
insignificant as compared with the water-soluble no means been fully exploited [3, 4].
substances. Cellulose ethers are produced by a Cellulose ethers can be sorted by their eco-
polymer-analogous reaction of cellulose with nomic significance. The most important prod-
low-molecular alkoxylating agents, which can ucts in terms of sales are carboxymethyl-
support further functional groups. celluloses (approx. 230 000 tons per annum),
The manufacture of cellulose ethers was first methyl- and hydroxyalkylmethylcelluloses (ap-
published in an article by W. Suida [1] in 1905 prox. 120 000 t/a), hydroxyethylcelluloses (ap-
and the first patents [2] relating to their indus- prox. 60 000 t/a) and hydroxypropylcellulose
trial production were issued as early as 1918. (less than 10 000 t/a). The demand is served by a
In the decade between 1920 and 1930 carboxy- small number of manufacturers, which employ
methyl cellulose was the first cellulose ether to proprietory processes and have developed their
gain economic significance, followed by methyl own areas of expertise.
celluloses and hydroxyethyl cellulose some ten
years later. These three product categories still
dominate the market today. 2. Properties
During the time cellulose ethers have been
used, continuous intensive research focusing on Cellulose ethers are nontoxic, usually water-
production processes and applications has been 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- crystal structure based on hydrogen bridges, the
uble in water, but their share of sales is insignif- partial imperfection of this structure caused by
icant as compared with the water-soluble sub- substituents results in free hydroxyl functions,
stances. hence first the substance becomes soluble in al-
The bulk density of cellulose ethers is bet- kalies and subsequently in water. Further ether-
ween 300 and 600 g/L. They are lightfast and ification with hydrophobic substituents results
their storage life is claimed by the suppliers to be in solubility in organic solvents and ultimately
between 18 and 36 months. Cellulose ethers turn thermoplasticity (intrinsic solubility).
brown at elevated temperatures (around 200 ◦ C) Alongside the hydrophilic-hydrophobic in-
and show signs of decomposition above 250 ◦ C. teraction which culminates in “thermodynamic
Their biodegradability can be influenced by the solubility”, the particle-size distribution has a
degree of substitution. crucial impact on the obtainable state of solution.
Cellulose ethers are capable of swelling or Particle size determines the kinetics of the disso-
are colloidally soluble; they increase the viscos- lution process. If the particles are too large, they
ity of the solvent and develop a specific rheolog- may not dissolve fast enough; they will swell
ical profile. Depending on the substitution, cel- and release some of their outer layer into the so-
lulose ethers in solution are surface-active (sur- lution; due to the rising viscosity the mobility
face tension: water 72 mN/m, carboxymethyl within the solution will decrease, leaving undis-
cellulose 70 mN/m, hydroxyethyl cellulose 63 solved particle residues which will no longer dis-
mN/m, methyl cellulose 54 mN/m). The non- solve in a reasonable time. Particles, that are too
ionic derivatives are film-forming substances, small, on the other hand, may cause formation
resulting in transparent films with a high elastic- of lumps during the dissolving process. Again
ity. Solutions and films obtained from cellulose this will ultimately result in undissolved parti-
ethers are compatible with other hydrocolloids. cle residues preventing formation of a homoge-
In many applications, however, where cer- neous solution.
tain properties of an initially dry mixture such as To counteract these problems, most suppliers
dissolving and solvent binding behavior (water issue recommendations as to which particle size
retention) are required, cellulose ethers are not is best for a particular application. Some suppli-
used in ready-made solutions, but are blended ers also offer specially treated products for en-
with other solids,. hanced dispersibility. These are mostly powder
These three characteristics – dissolving be- grades, whose initial dissolving rate is greatly
havior, the resultant solution structure, and the reduced (“delayed or retarded solubility”) to en-
cellulose ether’s capability of binding solvents – sure that the substance is homogeneously dis-
depend on molecular characteristics such as the tributed in the solvent before starting to dissolve.
type, number and distribution of the substituent This delay can be achieved, for instance, by a re-
and the molar mass distribution. versible cross-linkage with glyoxal. The rate of
In technical specifications generally only the dissolution is thus pH-dependent.
degree of purity, the viscosity in aqueous solu-
tion and in some cases the degree of substitution
are stated. 2.2. Solution State

The state of solution obtained, i.e., the sum of the

2.1. Swelling and Dissolving Behavior interaction between the cellulose ether and the
solvent and the intramolecular and intermolecu-
The different swelling and dissolving behav- lar interaction of the cellulose ether molecules,
ior of the various cellulose ethers originates determines the rheological profile of a solution
from the interplay of the hydrogen bonds bet- or of an end product.
ween free OH groups on the one hand and hy- The standard rheological models of polymer
drophilic and hydrophobic substituent groups on chains dissolved in coil formation can be used
the other. This interplay can be imagined as be- to describe the characteristics of cellulose ether
ing the gradual introduction of hydrophobic sub- solutions, depending on the intrinsic viscosity
stituents into native cellulose. Starting from a
 Cellulose Ethers 3

(also referred to as Staudinger index) and con- mass or chain length; the correlation is shown by
centration. All known polymeric solution states the Mark-Houwink equation. When the intrinsic
from the diluted particle solution to the con- viscosity is gauged, not only the molar mass is
centrated network solution [5] can thus be de- determined but also the quality or performance
scribed. However, on account of their inclina- of the solvent. Therefore effects attributable to
tion to form aggregates, cellulose ethers often pH, temperature and low-molecular salts, which
set scientists impossible tasks to solve. have a substantial impact on the solution struc-
The viscosity of a cellulose ether solution is ture, are also part of the analysis. Many cellu-
generally stated as a characteristic feature. Mea- lose ethers can be salted out by “removing” the
sured in a 2 wt% aqueous solution, it is some- hydration shell of the molecules. With the ionic
times included in the product grade designa- products, polyelectrolytic effects such as “repul-
tion for orientation purposes. At first glance this sion” or “cross-linking” due to the charging of
seems to be useful, because many application- the macromolecules among themselves or with
related properties are dependent on the same mo- the charges of salts present in the solution also
lecular parameters as viscosity. On closer, more need to be observed.
discriminating examination, however, this turns The maximum possible thickening effect is
out to be misleading, first because the dissolving predetermined by the used cellulose. The ac-
and measuring methods differ from one supplier tual viscosity achieved by a cellulose ether de-
to another, which can result in a similar product pends on how well chain scissions can be pre-
having twice the viscosity, and second because vented during the production process and on the
– although giving a rough guide – the viscos- type and quantity of substituents introduced into
ity does not describe the solution structure and the cellulose molecule. Each substituent repre-
seldom the product’s behavior in the final appli- sents an increase in molar mass without an in-
cation system. crease in the chain length. This reduces the thick-
In the range relevant to the applications the ening effect. The substituents are, of course,
viscosity of cellulose ether solutions rises dis- indispensable for solubility and other proper-
proportionately with increasing concentration ties; however, derivatives which predominantly
and intrinsic viscosity: carry substituents with a low molar mass and
where the degree of substitution is not too high
viscositysolution ∝ viscositysolvent • are particularly effective thickeners. The sub-
3.4
(concentration • intrinsic viscosity) a stituent group with the lowest molar mass is the
methyl group which simultaneously cancels out
(0.5< a < 1.0; a: exponent of the Mark- the intermolecular hydrogen bonds very effec-
Houwink equation) tively. As pure methyl cellulose manifests a spe-
Most solutions show a pseudoplastic behav- cific temperature-dependent dissolving behav-
ior, which is very important in practical terms. ior, which restricts its universal use, mixed cel-
Many cellulose ether solutions manifest time- lulose ethers with a low degree of substitution
dependent rheological functions, so the mea- with hydroxyethyl or hydroxypropyl groups are
surements depend on how the sample has been generally used as high-viscosity thickeners, for
pretreated. The elasticity of the solutions also instance in the construction sector.
increases with rising concentration and intrinsic The amount of cellulose ether used or its con-
viscosity, but the exponents are different from centration in an aqueous solution has a simi-
those of the viscosity function; therefore the cel- larly great effect as that of the chain length.
lulose ether selected can modify the ratio of When used as a thickener, the concentration
viscosity to elasticity within certain limits [6]. range employed is usually in the range of a mod-
Some application systems exhibit a solid-like erately concentrated network solution in which
behavior at low shear stress and viscous flow the polymer chains are not isolated but looped,
only starts at stress levels above the so-called forming a temporary physical suspension net-
yield stress (plastic flow behavior). work.
The intrinsic viscosity describes the volume The temperature dependence (below the floc-
“filled” by the free molecule. The intrinsic vis- culation point) of the flow behavior of aqueous
cosity is often used as a measure of the molar cellulose ether solutions follows the principle
4 Cellulose Ethers

of temperature-time superposition. At a higher secondary substitution is possible (methyl, car-

temperature all the molecules move faster. If a boxymethyl), the molar substitution (MS), i.e.,
flow curve (shear stress as a function of the shear the absolute number of substituents per anhy-
rate) is plotted at a reference temperature, the droglucose unit, is identical to the degree of sub-
flow curve determined at a higher temperature stitution (DS), i.e., the number of substituents
follows the same shear stress path, except that it directly linked to the anhydroglucose unit. In
is merely shifted to higher shear rates. Accord- the case of substituents containing hydroxyl
ingly, at the higher temperature the viscosity val- groups (hydroxyethyl, hydroxypropyl), for ex-
ues are on a lower level. ample, further (secondary) reactions with the
Changes in flow behavior are thus predeter- substituent can occur, i.e., there is no decrease in
minable (as long as there is sufficient distance the number of reactive centers. With these prod-
from the flocculation point). Therefore, when us- ucts a distinction has to be made between MS
ing the cellulose ether as a thickener in aqueous and DS. Comparing MS and DS shows the pro-
systems, the rheological behavior can be very portion of side-chain substitution. On account of
reliably estimated above and below the refer- the simpler analytics involved, frequently only
ence temperature, if the flow activation energy the MS is stated.
is known. In the case of many cellulose ethers To examine the characteristic features more
in aqueous solution the flow activation energy is precisely, it is necessary to analyze the sub-
in the proximity of 40 kJ/mol. Additional sub- stituent distribution. Primary substitution (i.e.,
stances dissolved in the water may cause a shift prior to any secondary reactions with the sub-
in this value, but there is no fundamental change stituent) already involves three kinds of distri-
in the correlations. bution:
• Substituent distribution within an anhy-
droglucose unit: depending on the reagent, the
2.3. Thermally Induced Coagulation
distribution can be between C-2, C-3, and C-6.
The solubility of cellulose ethers with hydropho- This distribution can be analyzed by means of
bic substituents like methoxy groups decreases nuclear resonance spectroscopy or hydrolysis
as the temperature rises, i.e., the performance and subsequent chromatography [8].
of the solvent deteriorates. Cellulose ether dis- • Substituent distribution along the backbone
solved in a cold solution can be made to co- chain: in contrast to the random distribution
agulate by heating the solution. The process is normally found, a strictly uniform substituent
reversible: when the solution cools down, the sequence along the chain or a block structure
cellulose ether dissolves again. Depending on formation are conceivable as theoretical bor-
the selected type and degree of substitution, the derline cases, which show up the different ef-
flocculation point of industrial used products is fects on solubility and therefore on the prop-
varied between 30 and 100 ◦ C. erties in general. To gain an impression of the
This is an important characteristic for indus- distribution along the chain, various break-
trial production of cellulose ethers because in down methods and subsequent liquid chro-
this way byproducts and salts can be washed out matography or derivatization and gas chro-
with hot water instead of with mixtures of water matography coupled with mass spectroscopy
and alcohol. are used to obtain the proportions of non-,
To assess the flocculation point with mixed mono-, di- and trisubstituted anhydroglucose
substituent groups, suitable flocculation dia- units. To assess the distribution of these units
grams have been published [7]. along the chain, the results of analysis of frag-
ments of various lengths can be compared.
Appropriate methods have so far only been
2.4. Degree of Substitution developed for particular derivatives and only
few research scientists have a good command
The type of substituent and the degree of substi- of them [9, 10].
tution determine most of the properties of a cel- • Substituent distribution between the individ-
lulose ether. With substituent groups where no ual chains: the substituent density can also
 Cellulose Ethers 5

vary between the individual chains of the cel- into account, some vital assertions can be made
lulose ether, one known example being the relating to existing systems. However, only in
nonsubstituted cellulose fibers in otherwise rare cases do the results stand up to compari-
clear-soluble products. With ionic products son (between various methods) in respect of an
the interchain distribution can be detected “absolute” molar mass distribution.
by polarographic analysis and an appropri-
ate method for other derivatives is chromatog-
raphy after specifically marking the free hy- 3. Production
droxyl groups. The problem with both meth-
ods is that the molar mass distribution has to Cellulose consists of chains of anhydroglucose
be known in order to carry out the assessment units (AGUs) linked together glycosidically (β-
[11]. 1-4-bonds) (→ Cellulose). Accordingly, each
AGU still has three free hydroxyl groups which
In the case of derivatives where a reaction vary in their reactivity and which can be con-
with the substituent is possible, the potential verted to ether groups in polymer-analogous re-
number of different anhydroglucose units and actions.
their distribution increases randomly, and the The free hydroxyl groups form intermolecu-
structure becomes enormously complex. At the lar and intramolecular hydrogen bonds, so be-
same time, however, the possibilities for adapt- fore the cellulose can be etherified it needs to
ing the hydrophilic-hydrophobic interaction to be ‘activated’. For this purpose the cellulose
suit individual applications increase as well. is chemically converted, usually with sodium
hydroxide solution (caustic soda), in order to
open up its natural structure and to obtain a suf-
2.5. Molar Mass Distribution ficiently swollen material that is accessible to
further reagents. The outcome is known as al-
Knowing the molar mass or the molar mass dis- kali cellulose or soda cellulose. The degree of
tribution makes it possible in theory to access swelling is controlled by the ratio of sodium hy-
various material functions. An absolute deter- droxide solution to cellulose and by the method
mination of these variables has so far only been of adding suspending agents or swelling agents.
achieved in isolated cases and with an enor- A minimum quantity of alkali (approx. 0.8 mol
mous research input. Due to the “poor solubility” per mole of AGU) is required to swell the cellu-
and the propensity of most derivatives toward lose and for the reagents. During this activation
association, producing time-stable molecularly process several properties of the end product are
disperse solutions is only rarely possible. Fre- predetermined, because the degree of swelling
quently it is a mixture of molecules, associates and the uniformness of the activation influence
and aggregates that is analyzed, and the results the distribution of the substituents introduced in
are often impossible to interpret reliably. the second stage of cellulose ether production.
It is precisely because of this complexity that After the cellulose has been activated, the
so many attempts to make a breakthrough have etherifying reagent is added. In principle, any
been launched in the past, starting with “batch etherification reaction known in the context of
methods” such as static and dynamic light scat- low-molecular alcohols could be applied, many
tering in many different solvents, and “classify- of which have been studied [3]. Two basic types
ing” methods such as ultracentrifugation, size- have become established in the industrial pro-
exclusion chromatography and flow-field-flow duction of cellulose ethers – reactions where
fractionation, and also combined methods in- sodium hydroxide solution is consumed (e.g.,
volving chromatography and various detection Williamson ether synthesis) and reactions where
systems. All these approaches have in common sodium hydroxide only acts as a catalyst (e.g.,
that, although they give an interesting insight alkoxylation). The supernatant caustic solution
into the solution structure, the results often de- is neutralized after the reaction.
pend on how the samples have been prepared and The kind of cellulose and its quality are cru-
how they are influenced by the measuring pro- cial with regard to the ultimate properties of the
cedure itself. Taking the measuring conditions cellulose ether. Therefore, many different types
6 Cellulose Ethers

of cellulose obtained from wood pulp or cot- tanks made handling more difficult and reduced
ton linters are used. The type of cellulose used its processability.
determines, among others, the maximum chain To make the cellulose more accessible to the
length, hence the viscosity yield of the final cel- chemicals involved, in modern processes the cel-
lulose ether. The chain length is reduced on ac- lulose is generally ground or milled before the
count of the chemical and thermal stresses im- activating and reaction stages. The cellulose is
posed during the process. The incidence of chain then alkalized with highly concentrated (approx.
scissions is inherent in the production process 30 – 70 wt%) aqueous caustic soda solution. Al-
but can be selectively increased. Oxidative, acid kalization usually takes place in mixers or stirred
and radiation-induced decomposition are some reaction vessels, depending on the mass fraction
of the known degradation processes which, de- and the reaction system. The mass fraction can
pending on the product category, are used at var- be selected to influence the water balance which
ious points in the process to obtain a desired low affects side reactions or reagent yield and also
viscosity. the quality of the cellulose ethers. The way the
Processes. The processes depend on the chemical reaction is engineered during the alka-
synthesis-related reaction stages which can take lization stage also has a significant effect on the
place in one set of equipment or in several sets quality of the cellulose ethers (see above).
arranged in sequence. The reaction can be carried out either batch-
A distinction is made between reactions at wise, semibatchwise (fed batch) or continu-
ambient pressure and reactions carried out at up ously, and the reaction temperatures vary from
to 30 bar, depending on the different reagents room temperature up to 110 ◦ C, depending on
and on the required weight percentage of cellu- the type of etherification. Here again, mixers
lose or cellulose ether in the reaction medium and stirred vessels are the established equip-
(mass fraction). Heterogeneous syntheses are ment. There are some isolated patents describing
used for industrial-scale production, whereas continuous processes in different equipment set-
homogeneous syntheses are so far only found ups [14 – 16]. The starting materials are fed as
in research. Heterogeneous systems are clas- solids or liquids under pressure. In some older
sified by mass fraction into suspension pro- processes for the production of methyl or hy-
cesses (mass fraction below 10 wt%) and slurry droxyalkylmethyl celluloses gaseous reagents
processes (mass fraction approx. 10 – 50 wt%). are used.
There is also the option of a gas-phase or vapor- The equipment assembled downstream of
phase process, that works without an inert liq- the reaction depends on the required degree
uid. The process technology and engineering is of purity. In general a distinction is made bet-
adapted to meet the requirements of the mass ween technical and nontechnical cellulose ethers
fraction involved. which differ in their content of byproducts and
The cellulose is usually supplied as rolls of neutralization products – predominantly salts.
cellulose webs or as cellulose sheets. In the early Depending on the washing agents and the type of
days of cellulose ether production, the cellu- wash (displacement or dilution-type wash) the
lose was treated in an alkali bath (approx. 15 equipment used for solid-liquid separation in-
– 20 wt% caustic soda) with the disadvantage cludes suction filters, belt filters, drum filters,
that the cellulose had not been ground and was centrifuges and decanters, operating either con-
therefore not fully accessible to the activating tinuously or batchwise. The washing processes
agent. Consequently, the activation process took are carried out in aqueous or alcoholic media,
4 h and the ripening time 8 h or more [13]. Dur- depending on the product group.
ing the ripening process the alkali cellulose was If the product is still wet with solvent after the
kept in intermediate tanks where the reaction washing sequence, the inert dissolving or wash-
was allowed to complete at a specific temper- ing agents can be recovered by displacing them
ature. Prior to the ripening stage any excess ac- with water prior to the drying stage. Suitable
tivating agent was pressed out and the alkali cel- equipment for this are, for example, continuous
lulose was then shredded. Storing it in ripening mixers. Auxiliary facilities are used for regen-
erating the reagents and washing media and for
extracting byproducts.
 Cellulose Ethers 7

At the end of the process line the products are specific differences in definition. Products with
converted in forming stages from their fibrous an active content of 55 – 85 % are considered
form into the required supply form, usually pow- to be “unpurified”; 85 – 95 %: “semi-purified”;
der grades with a defined particle size distri- around 98 %: “purified”; and products with an
bution and containing small amounts of resid- active content greater than 99.5 % are classed as
ual moisture (in most cases < 10 wt%). Various “highly purified” (high-purity grades).
drying and comminuting equipment is used in a Annual sales worldwide amount to approx.
number of different combinations. This process 230 000 t, of which purified CMC accounts for
step is also utilized for modifying the cellulose 130 000 t and unpurified CMC totals 100 000 t.
ethers so that they offer optimal properties for It is difficult to accurately apportion figures to
the individual fields of application. The parti- the two segments, not only because of varying
cle size distribution ranges from granular grades definitions but also due to the fact that in some
with an average grain diameter of approx. 0.5 applications both purified and unpurified grades
mm to very fine powders where the percentage of CMC can be used, and many suppliers have
of particles with a diameter of less than 63 µm both purified and unpurified products in their
is higher than 50 wt%. portfolios.
CMC can be produced with less technologi-
cal input than the other cellulose ethers, which
4. Product Groups explains why a comparatively large number of
manufacturers (more than 20) exists. The lead-
4.1. Carboxymethyl Cellulose (CMC) ing producer is CP Kelko with a market share
of around 33 %. The largest regional market and
In terms of sales volume carboxymethyl cellu- the region with the largest production capacity is
loses are the largest product group. They are currently Europe, which still accounts for some
available in various levels of purity from com- 60 % of global capacity.
pletely “unpurified” to “highly purified” for The initial application fields of CMC were
food-grade applications. The CMC group also detergents, where it acts as a soil carrier, and
includes mixed ethers with hydroxyalkyl sub- in deep-well drilling for oil and water, where it
stituents, that have a predominantly ionic char- is used as a flotation aid in drilling mud. Un-
acter. The structure of CMC is shown in Figure 1. 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
Figure 1. Structure of CMC 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-
4.1.1. Applications / Market tency and to provide a low-calorie replacement
for starch and proteins, or to control more com-
The market can be divided into two segments: plex functions such as the freeze-thaw stability
one for “purified” and another for “unpurified” of deep-frozen products or the creaminess of ice
CMC. However, the terms “purified” and “un- cream.
purified” are subject to regional and supplier-
8 Cellulose Ethers

4.1.2. Synthesis In contemporary CMC production processes

the ground cellulose is processed batchwise ei-
CMC is produced in a Williamson ether synthe- ther as a suspension in the case of a low mass
sis from alkali cellulose with sodium chloroace- fraction of cellulose or, if the mass fraction is
tate or with chloroacetic acid itself, which reacts high, in mixers in the presence of “inert” me-
in-situ with caustic soda to form the salt. The dia (see Fig. 2). Both processes use one or
process takes place in an aqueous or aqueous- more short-chain alcohol(s) as a mass-transfer
alcoholic medium (slurry). The alcohols used and heat-exchanging medium or as a suspending
are ethanol, isopropanol, tert-butanol and mix- agent. For processes with a high mass fraction
tures thereof. ethanol is usually employed a slurry medium,
whereas isopropanol is used in suspension-type
Cell−OH·NaOH+ClCH2 COONa→
processes [20, 21]. By placing several sets of the
Cell−O−CH2 COONa+NaCl+H2 O
same kind of equipment in parallel or in series
Alkalyzation is carried out at room temper- it is possible to implement a quasi-continuous
ature; the reaction takes place between 50 ◦ C operation in the activation and reaction stages.
and the boiling point of the slurry medium un- The starting materials and suspension or
der appropriate system pressure. The reaction slurry media are either solid or liquid at normal
is exothermic. With an activation energy of room and reaction temperatures. Activation and
87.9 kJ/mol it is highly temperature-dependent. reaction can therefore be carried out at ambient
The yield from this reaction in relation to pressure.
chloroacetic acid is between 65 % and 80 %. Hy- Depending on the required product purity, the
drolysis of chloroacetic acid occurs as a side re- product is washed with alcohol-water mixtures,
action, forming glycolate. Commercial CMCs preferably with the same alcohol used in the re-
are produced with a degree of substitution bet- action. Washing with water is not possible be-
ween 0.2 and 1.5. Carboxymethylation takes cause of the water-solubility of the products. To
place with a slight preference toward C2- fol- meet product purity requirements, it is necessary
lowed by C6- and C3-substitution of the anhy- to remove the alcohols from the product after the
droglucose unit [17]. washing stage and prior to the grinding and dry-
ing processes.
Suspension agents and washing liquids are
4.1.3. Processes collected and reprocessed either by distillation
and extraction or membrane 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 4.1.4. Characterization
been pressed out and the alkali cellulose had
been shredded to fibers, the reaction was carried Carboxymethyl cellulose becomes water-
out with the addition of sodium chloroacetate in swellable or alkali-soluble even at a low degree
a kneader, where temperatures reached 30-35◦ C. of substitution. The water-solubility of industri-
The reaction was completed in a tumbling drum ally produced CMC begins at a DS of approx.
at 50 ◦ C. The material was then washed with a 0.6. The solubility increases up to a rather the-
mixture of methanol and water, filtered, ground oretical DS value of 3.0. Research work has
and finally dried. shown that products with a lower degree of
The first continuous process was used by substitution (DS < 0.6) can manifest good sol-
Wyandotte Chem. Corp. (1947), but there was no ubility, the reason being different substituent
washing stage, so it was only suitable for unpuri- distribution along the backbone [22].
fied CMC [19]. Sodium hydroxide solution and Aqueous carboxymethyl cellulose solutions
monochloroacetic acid were added to the ground have very complex solution structures, because
cellulose in a rotating drum. After a dwell time boundary conditions such as pH or salts simulta-
of 3 h the product was allowed to “ripen” for 10 neously affect various characteristics. The solu-
h in drums. tion state achieved depends, as with other cellu-
lose ethers, on the nature of the dissolution pro-
 Cellulose Ethers 9

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- The many different possibilities of micro-
rameter “solvent performance” covers all ther- scopic interaction are also reflected in the macro-
modynamic effects of protons, salts and other scopic properties of CMC. From a rheological
low-molecular substances on the interaction bet- point of view CMC solutions are inclined to
ween the solvent and the macromolecule. form superstructures. Viscosities of 2 wt% so-
In addition CMC is a weak carboxylic acid. lutions ranging from 3 mPa·s to 100 000 mPa·s
The proton concentration in the solution not only are available on the market. Most of the prod-
affects the solvent’s performance but simulta- ucts exhibit pseudoplasticity, some of them a
neously alters the number of free carboxylate thixotropic behavior. Depending on the selected
groups. CMC’s equivalence point is at a pH of degree of substitution and the product group,
8.25; its pK a value is between 4 and 5. In its acid the solutions are either smooth-flowing or highly
form CMC is insoluble in water. Depending on gelatinous.
the degree of substitution CMC can be precip- Commercial grades are not only categorized
itated from the solution at low pH values. De- according to their purity, their morphology and
protonation increases with rising pH values and their mean viscosity, but also according to their
the character of the polyelectrolyte becomes ap- degree of substitution. Water-soluble CMC com-
parent: The repulsion among the individual sub- modities are available with a DS of around 0.7,
stituents becomes more distinct and the salt sen- 0.9 and 1.2. These three product groups do not
sitivity increases. When CMC comes into con- only differ in their DS, but also in their solution
tact with selected divalent or trivalent salts, this structure, hence their rheological behavior.
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].
10 Cellulose Ethers

4.2. Methyl and Hydroxyalkyl Methyl low additive contents of between 0.01 and 2 wt%
Celluloses (in relation to the building material system). Ac-
cordingly, the cellulose ether has to meet high
Pure methyl cellulose (MC) and hydroxyalkyl quality requirements.
methyl celluloses (HAMC) are collectively In the life-science sectors only nonhy-
known as methyl cellulose. Pure methylcellu- droxyalkylated methyl cellulose (modified veg-
lose only accounts for a minor share of the etable gum) and hydroxypropyl methyl cellulose
market. The mixed ethers hydroxyethyl methyl (carbohydrate gum) are used. In the pharmaceu-
cellulose (HEMC, see Fig. 3) and hydroxypro- tical industry methyl celluloses are employed as
pyl methyl cellulose (HPMC) have established tablet base and in coatings of controlled-release
themselves in particular for technical applica- drugs. In the food and cosmetics industries it is
tions. 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

Figure 3. Structure of HEMC 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
4.2.1. Applications / Market solution is consumed, whereas alkylation only
requires catalytic amounts of alkaline solution.
The market for methyl cellulose and hy- Pure MC is produced from alkali cellulose by
droxyalkyl methyl celluloses was in the range a reaction with gaseous or liquid methyl chlo-
of 120 000 t in 2003, the market leader being ride. In side reactions the methyl chloride is hy-
Dow Chemical Company, with Shin-Etsu Chem- drolyzed to form methanol, and subsequently the
ical and Wolff Cellulosics having slightly lower methanol is etherified by methyl chloride, form-
market shares. High-purity grades are marketed ing dimethyl ether. The reactions take place bet-
for applications in the food, pharmaceutical and ween 70 and 120 ◦ C. Methylation is an exother-
cosmetics sectors and purified products are used mic reaction, the activation energy being 80
in building materials and industrial applications. kJ/mol.
The building material segment is by far the
largest field of application. Cell−OH·NaOH+ClCH3 →Cell−O−CH3 +NaCl+H2 O
The applications and therefore also the types
The grades produced have a degree of substi-
of product used in the building materials sector
tution of 1.7 and 2.3. In case of pure methylation
vary from region to region due to different con-
the substituent is found to prefer C2-, followed
struction methods and traditions (→ Dry Mor-
by C6- and C3-positions of the anhydroglucose
tars). In the USA joint compounds account for
unit [25, 26].
the largest segment; in Europe the main appli-
In the course of hydroxyalkyl methyl cel-
cations of MC and HAMC are plasters, renders,
lulose production alkoxylation of the cellulose
and tile adhesives. Efficient modern application
takes place prior to or parallel to its methyla-
methods would not be possible without the use
tion. As both the cellulose and the alkoxy groups
of methyl celluloses. Properties such as water re-
formed can be methylated and alkoxylated, the
tention, open time, wet adhesion, initial thicken-
outcome is a potentially indefinite number of
ing and setting behavior are regulated using only
 Cellulose Ethers 11

different products, allowing the range of proper- dissolved and any nonreacted activation reagents
ties to be tailored to the requirements of specific are neutralized with acid. The suspension is then
applications. separated in a solid-liquid separating unit. Fur-
ther washing stages may be required, depending
on the product specifications, in order to comply
4.2.3. Processes reliably with restrictions in content of byprod-
ucts.
The development of processes to produce methyl Again depending on the type of product, the
cellulose and hydroxyalkyl methyl celluloses HAMC is then conditioned for the grinding and
began with methods at ambient pressure, i.e. drying stage. Drying and grinding can be carried
gas circulation processes, where the cellulose out in succession or in combined milling and
is activated (for example by a steeping process), drying units. The required fineness of grind, i.e.,
shredded and subsequently brought into contact the particle size, which in some cases is less than
with the reagents in a mixer. Nonreacted gaseous 63 µm in more than 50 wt% of the product, can
feed materials and byproducts are continuously often only be achieved in screening and sifting
extracted, the byproducts are condensed out and stages, after which the coarse-grained material
the gas flow is returned to the reactor. The prod- is recycled.
uct is then washed, filtered, compressed, ground
and dried.
The slurry process (see Fig. 4), operated 4.2.4. Characterization
at pressures of up to 30 bar, is the process
in most widespread use today for producing With a degree of substitution of around 1, methyl
HAMC batchwise or semibatchwise in a mixer. celluloses exhibit good water solubility at room
Processes patented in the 1950s suggest the temperature. The higher the degree of substitu-
use of pressure-resistant reactors without any tion, the better the solubility in water. However,
additional inert slurry media [27]. More re- it decreases again with further methylation and
cent patents propose adding inert slurry media, changes to solubility in organic solvents at a DS
mostly ethers [28]. The slurry medium acts as a of approx. 2.6, because the material becomes in-
heat-transfer medium, which evaporates and is creasingly hydrophobic.
condensed in a dome-shaped condenser. Available on the market are pure methyl cel-
The reagents are added to the ground cellu- luloses with a degree of substitution between
lose in any sequence, depending on the targeted 1.7 and 2.3, hydroxyethyl methyl celluloses
product characteristics. The slurry medium has with methylation levels between 1.3 and 2.0
to be added prior to etherification on account and ethoxylation levels between 0.1 and 0.4,
of the heat generated during the exothermic re- and hydroxypropyl methyl celluloses with de-
actions. Once the reaction has been completed, grees of methylation between 1.3 and 2.1 and of
low-boiling slurry media are extracted by re- propoxylation between 0.1 and 1.0. The limits of
ducing the pressure and are collected for reuse. substitution are more or less predetermined by
Byproducts are discharged. High-boiling slurry the products’ flocculation point, because wash-
media are separated during the washing stage ing with water is less expensive than with alco-
and subsequently reprocessed. hol.
Suspension-type processes are mentioned in The flocculation point, i.e., the gelation and
several patents. Their advantages are their sim- subsequent coagulation as the temperature rises,
ple process engineering, whereas disadvantages is a characteristic found only in nonionic cellu-
can be seen in the more complex preparation of lose ethers. By varying the methyl and/or alkyl
the suspension agent. content of hydroxyalkyl methyl celluloses, it is
The flocculation point of MC and HAMC al- possible to modify the macromolecule’s affinity
lows the products to be washed with water above to its water shell and therefore the flocculation
this flocculation point. To do so, the contents of point: with increasing methyl substitution the
the reactor are led into a stirred tank filled with number of hydrophilic groups is reduced, and
hot water or they are suspended in the reaction the flocculation point drops. Accessibility to the
mixer; the salts formed during the reaction are 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 spraying highly concentrated solutions and for
point shifts to higher temperatures. (The intro- good leveling and film formation.
duction of hydroxypropyl substituents results in HEMC or HPMC grades with a higher vis-
opposite characteristics where, depending on the cosity for use as thickeners, however, exhibit
degree of substitution, the flocculation point ei- a non-Newtonian flow behavior even with at
ther rises or drops.) Especially for applications low concentrations. In building materials appli-
where there is a high ambient temperature, e.g. cations, such as tile adhesives, the high static
on building sites in the summer, a methyl cellu- shear viscosity guarantees standing strength and
lose (MHEC or MHPC) with a sufficiently high resistance to demixing as well as high water re-
flocculation point should be used to eliminate tention, while the non-Newtonian properties en-
any undesired changes in characteristics. sure rapid and easy workability. The thickening
The rheological properties of methyl cellu- characteristics of nonionic cellulose ethers are
loses and hydroxyalkyl methyl celluloses vary scarcely affected by the presence of dissolved
within a broad range, exhibiting some very dif- (even polyvalent) salts or by changes in the pH
ferent features, because there is a wide viscosity value, so they are also ideal for use in cement-
range in the grade spectrum available and be- based building materials in which, after water is
cause the products can have very differing chem- added, highly alkaline conditions prevail.
ical structures. The most effective way to achieve good thick-
Products with a particularly low viscosity, ening at a low shear rate is to use small input
such as HPMC for tablet coatings with a typ- quantities of high-viscosity grades. In these sys-
ical viscosity of between 3 and 6 mPa·s at a tems the viscosity soon drops considerably as the
concentration of 2 wt% in water, still show a shear rate increases. A high thickening effect at
purely Newtonian (ideal) flow behavior in aque- high or at least at medium shear rates is desirable
ous solutions with a HPMC concentration of 10 for improved workability in certain high-quality
– 20 wt% at room temperature, and the viscos- building material systems, and it can only be
ity of these solutions can be as high as 10 000 obtained with higher levels of methyl cellulose,
mPa·s. The Newtonian behavior is crucial for which also provide additional benefits, such as
 Cellulose Ethers 13

long open times and improved adhesion in the hydrophobically modified grades are, like purely
case of tile adhesives. synthetic associative thickeners, capable of pro-
viding additional effects by interacting with par-
ticle surfaces, in particular those of the binder in
4.3. Hydroxyethyl Cellulose (HEC) [29] latex paints, and by forming micelles and mixed
micelles with other surfactants contained in the
Hydroxyethyl celluloses are the third largest paint. These options are exploited especially in
product group in the marketplace. They are non- high-grade paint formulations in order to reduce
ionic and soluble in both cold and hot water. spattering when applying the paint with a roller,
Their manufacture was first described in 1920 and to obtain improved brush resistance and lev-
in a patent granted to Farbenfabriken Bayer. The eling.
structure of HEC is shown in Figure 5.

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−
Figure 5. Structure of HEC
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-
4.3.1. Applications / Market colates formed in the process. Large amounts of
alkali reduce the yield of the main reaction, but
The hydroxyethyl cellulose market is served to produce HEC a minimum quantity of caus-
mainly by Hercules Incorporated/Aqualon and tic soda solution is essential to break down the
Dow Chemical Company. Annual sales are cellulose.
around 60 000 t, most of which are used in the Ethoxylation takes place in the presence of
construction industry, and specifically in sur- an “inert” solvent (isopropanol, tert-butanol,
face coatings. Hydroxyethyl cellulose is also 1,2-dimethoxyethane or acetone); it starts at a
found in cosmetic applications where it com- very low temperature (≈ 30 ◦ C) and is highly
petes against HPMC derivatives. Other applica- exothermic. HECs are produced with a molar
tions are in drilling fluids and as a protective substitution of 1.5 and 3.5, these degrees be-
colloid in emulsion polymerization. ing controlled via the quantity of ethylene oxide
In the paint industry HEC is the cellulose added. The yield is between 40 and 75 % in rela-
ether product group with the largest market tion to ethylene oxide. The reaction of ethylene
share. Although products based on HEMC, oxide takes place in the following order of pref-
HPMC or CMC have smaller shares, they are erence (from high to low): alkoxy groups, then
firmly established in these applications for tech- C6 positions, then (followed by some distance)
nical and cost-related reasons. Beside pure HEC C2 and C3 positions [31]. The relationship of the
this product group also includes mixed cellu- reaction rates can be influenced by varying the
lose ethers similar to HEC: ethyl hydroxyethyl alkali concentration, e.g., by partial neutraliza-
cellulose (EHEC) and hydrophobically modified tion [32]. After the reaction has taken place, the
(hm) variants of HEC. The additional hydropho- alkali quantity added needs to be neutralized.
bic properties are imparted to hm-HEC by minor
secondary substitution, for instance with long-
chain alkyl residues (C12 through C24 ) [30]. The
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- Hydroxyethyl celluloses are available on the
cesses above ambient pressure have become the market with viscosities between 10 mPa·s and
established methods [33]. Stirred pressure ves- 100 000 mPa·s and molar substitutions of 1.5
sels are used for the reaction (see Fig. 6). and 3.0 (up to 4.5 in the case of hydrophobi-
The ground cellulose is suspended in the sus- cally modified grades). They are water-soluble
pending medium and mixed with the alkalizing and have no thermal flocculation point. Hydrox-
agent. After alkalization, liquid ethylene oxide yethyl celluloses are also more difficult to salt
is added to the suspension and allowed to react out than methylated derivatives and are not dis-
for about 2 h. placed from water even by larger amounts of or-
Salts and byproducts have to be washed out ganic solvent. The degree of substitution varies
of the products. As with other cellulose ethers, in the region of 1 in industrially produced grades,
this involves appropriate equipment for washing i.e., higher hydroxyethylation leads chiefly to
and solid-liquid separation either in series or in secondary, tertiary, and quaternary substitution
a combined unit. As this cellulose ether does not of the hydroxyalkyl substituent (formation of
have a flocculation point, mixtures of water and ethylene oxide side chains).
an organic solvent are used, followed by drying The rheological behavior of HECs is com-
and grinding. parable with that of carboxymethyl celluloses.
Parallel to this, the suspension medium and By introducing a small number of hydrophobic
any extracting agents have to be regenerated and side chains, grades can be obtained, whose rhe-
recycled. Distillation is the method usually se- ological profile in solution is highly modified,
lected for this.
 Cellulose Ethers 15

particularly when mixed with surfactants. The cellulose is activated with caustic soda solution.
hydrophobic residues form part of the surfac- The reaction has a somewhat higher activation
tant micelles and this increases the viscosity, es- energy and requires a higher reaction temper-
pecially at elevated shear rates. ature than that with ethylene oxide. The by-
products are propylene glycol and polypropyl-
ene glycols which, like the salts from the neu-
4.4. Hydroxypropyl Cellulose (HPC) tralization stage, need to be removed in one or
several washing stage(s).
In relation to the quantities of cellulose ethers
used worldwide, hydroxypropyl celluloses are
the smallest product group. Their properties 4.4.3. Processes
range from simple swellability, through solu-
bility in cold water to enhanced thermoplas- The production processes for HPC are largely
ticity, which enables them to be processed in the same as for HEC. The reaction is gener-
melt extruders. Hydroxypropyl cellulose was ally carried out in a slurry. The slurry media de-
first launched on the market in the USA at the scribed in relevant literature are hexane, toluene,
end of the 1960s. The structure of hydroxypro- tetrahydrofuran and dioxane, and also the com-
pyl cellulose is shown in Figure 7. 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

Figure 7. Structure of HPC 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
4.4.1. Applications/Market mPa·s. HPC solutions are generally smooth-
flowing and exhibit scarcely any tendency to-
The annual global market for hydroxypropyl cel- ward thixotropic behavior. Gelation and coagu-
lulose is far below 10 000 t. The main fields of lation begins at relatively low temperatures (40
application are in the pharmaceutical and cos- – 50 ◦ C). Hydroxypropyl cellulose is surface-
metics industries [34]. High-purity grades are active and tends to foam. Highly concentrated
available for food and pharmaceutical applica- HPC solutions can develop liquid-crystalline
tions, and purified grades are supplied to the cos- phases. With a sufficiently high degree of substi-
metics industry and for technical applications. tution hydroxypropyl cellulose is thermoplastic
Hydroxypropyl cellulose is supplied by and can be processed at approx. 150 ◦ C. The ex-
Hercules Incorporated/Aqualon, by Shin-Etsu truded moulded parts are water soluble yet, due
Chemical and by Nippon Soda. 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-
4.4.2. Synthesis ween 0.2 and 0.4, on the other hand, swells in
water, but is not water-soluble. These grades are
The synthesis of hydroxypropyl cellulose does used as binders or disintegrants in the manufac-
not differ from that of hydroxyethyl cellulose. ture of tablets.
Prior to the reaction with propylene oxide, the
16 Cellulose Ethers

5. Uses followed by hydroxyethylcelluloses on third

place with approx. 60 000 t/a and last by hy-
Cellulose ethers are used in a wide variety of droxypropylcellulose with less than 10 000 t/a.
fields ranging from oil drilling to industrial ap- Taking all market segments together, the cel-
plications such as polymerization, from surface lulose ether market has grown continuously in
coatings and construction materials to the health recent years. However, there has been and still is
care sector, cosmetics, food and pharmaceuti- a noticeable shift among the individual markets.
cals. Not all types of cellulose ethers are equally As opposed to vigorous growth in the threshold
suitable in all fields of application. Table 1 pro- countries and moderate growth in Europe and
vides an overview of the great variety of appli- the USA, the Japanese market is dwindling.
cations and the appropriate types of cellulose The market is served overall by a small num-
ether. A listing of this kind can only be incom- ber of suppliers of cellulose derivatives. Most
plete, but indicates the versatility and above all of the manufacturers produce a variety of differ-
the adaptability of the products to the various ent products for several market segments. The
fields in which they are to perform. carboxymethyl cellulose market is spearheaded
In many cases the amount of cellulose ether by CP Kelko, a company with a market share of
required is only between 0.02 and 2 %. This 33 %. The remaining market is shared by 10 to 15
small level is, however, crucial for properties small to medium-size suppliers. The methyl and
such as water-binding capacity, film formation hydroxyalkyl methyl cellulose market is served
and thickening as well as for controlling other by a few major producers [Dow Chemical Com-
rheological properties. Many modern products pany, Wolff Cellulosics, and Shin-Etsu Chemi-
and processing techniques would not be possi- cal (incl. SE Tylose, the former cellulose ether
ble without the use of cellulose ethers. division of Clariant AG)] with a market share to-
Each field of application requires specific so- taling 80 %. Hydroxyethyl cellulose is supplied
lutions which in many cases involve modify- more or less exclusively by Hercules and Dow
ing the cellulose ether product. This means that, Chemical Company, whereas HPC is mostly
once a suitable product category has been se- supplied by Hercules and Shin-Etsu Chemical.
lected, all the parameters relating to the appro-
priate type of substitution and viscosity range
have to be fine-tuned. Besides their chemical 7. Toxicology and Occupational
structure, characteristics such as product purity
and forming, i.e., the physical state in which the Health
products are made available, play a substantial Toxicology. Cellulose ethers are generally
part. Fine-tuning requires a great deal of experi- nontoxic. High-purity grades of most commer-
ence in respect of the properties of these products cial products are approved as food additives and
as well as with regard to the systems and meth- for use in cosmetic compositions.
ods of application. Most suppliers provide this Handling. Fine powders of cellulose ethers
expertise and offer additional technical service. form explosive dusts in air as do natural polysac-
charides or sawdust. Dry nonionic ethers un-
dergo electrostatic charging similar to that of
6. Economic Aspects other organic polymers. When cellulose ethers
are stored and handled, the general precautions
In 2003 the sales volume of the cellulose ether
concerning powdered organic polymers must be
market worldwide was approximately $ 2 ×
observed. The flammability is similar to that of
109 . The largest market is Europe, followed by
cellulose. Spilling of solutions forms very slip-
the USA and Japan. Annual consumption is ca.
pery films that are difficult to remove.
420 000 t.
Sorted in the order of their economic sig- Ecology. The biodegradation of cellulose
nificance (by sales volume), carboxymethyl- ethers by cellulase-producing microorganisms
celluloses rank first with approx. 230 000 also occurs in wastewater and therefore prevents
t/a, while methyl- and hydroxyalkylmethyl- the accumulation of cellulose ethers. Glucose,
celluloses are second with approx. 120 000 t/a, 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 10. P. W. Arisz: “Substituent distribution along the
to carbon dioxide and water in slow bioreactions. cellulose backbone in O-methylcelluloses
Biostable or toxic metabolites are not known. using GC and FAB-MS for monomer and
Cellulose ethers have no fish toxicity and are oligomer analyses”, Carbohydr. Res. 271
poor nutrients for most microorganisms. Nev- (1995) 1–14.
ertheless, wastewater bacteria may adapt to en- 11. B. Reiche, H. Jehring, H. Dautzenberg, B.
hanced cellulose ether degradation after some Philipp: “Elektrosorptionsuntersuchungen an
exposure. Carboxymethylcellulosen”, Faserforschung
und Textiltechnik 29/5 (1978) 324–328.
The suppliers provide Safety Data Sheets
12. “Cellulose”, in: Ullmann, 6th ed., vol. 6,
containing detailed data with regard to handling
WILEY-VCH Verlag GmbH, Weinheim 2002,
and the toxicological properties of the respective pp. 593–645.
products. 13. O. Wurz: Celluloseäther - Herstellung und
Anwendung, Roether, Darmstadt 1961.
14. Kalle AG, DE 1543136, 1969 (F, Eichenseer,
8. References S. Janocha, H. Macholdt ).
1. W. Suida, Monatshefte Chemie 26 (1905) 15. Dow Chemical Company, US 4015067, 1975
413–427. (G.Y.T Liu, C.P. Stange).
2. E. Jansen, DE 332203, 1918. 16. Henkel KgaA, DE 2929011, 1981 (W. Willi,
3. D. Klemm, et al.: Comprehensive Cellulose H. Leischner, W. Rähse, F.-J. Carduck, N.
Chemistry, Vol. 2, WILEY-VCH Verlag Kühne).
GmbH, Weinheim 1998. 17. H. M. Spurlin, J. Am. Chem. Soc. 61 (1939)
4. J. Schurz, et al.: “Methodische Fortschritte in 2222.
der Instrumentalanalytik”, Das Papier 12 18. J. Voss: “Celluloseäther”, in
(1999) 712–764. Kunststoffhandbuch, vol. 3, Hanser, München
5. W. W. Graessley, Polymer 21 (1980) 258. 1965 pp. 349–397.
6. W.-M. Kulicke, et al.: “Characterization of 19. R. N. Halder, W. F. Waldeck. F. W. Smith, Ind.
aqueous carboxymethylcellulose solutions in Eng. Chem. 44 (1952) 2803.
terms of their molecular structure and its 20. V. Stigsson, G. Kloow, U. Germgård,
influence on rheological behaviour”, Polymer PaperAsia 17/10 (2001) 16–21.
37/13 (1996) 2723–2731. 21. R. Dönges, Das Papier 12 (1997) 653–670.
7. R. Dönges, Das Papier 12 (1997) 653–670. 22. T. Heinze, T. Liebert, P. Klüfers, F. Meister:
8. P. Käuper, et al.: “Development and evaluation “Carboxymethylation of cellulose in
of methods for determining the pattern of unconventional media”, Cellulose 6 (1999)
functionalization in sodium 153–165.
carboxymethylcelluloses”, Angew. Makromol. 23. P. Käuper: “Natriumcarboxymethylcellulose:
Chem. 260 (1998) 53–63. Bestimmung der chemischen Struktur, der
9. P. Mischnick, et al.: “Structure Analysis of Lösungsstruktur und der
1,4-Glucan Derivatives”, Macromol. Chem. Elektrolytwechselwirkungen”, Berichte aus
Phys. 201 (2000) 1985–1995. der Chemie (1998), Shaker, Aachen.
18 Cellulose Ethers

24. “Dry Mortars”, in: Ullmann, 6th ed., vol. 11, 30. L.-M. Zhang, Carbohydr. Polym. 45 (2001)
WILEY-VCH Verlag GmbH, Weinheim 2002, 1–10.
pp. 83–108.. 31. M. G. Wirick, J. Polym. Sci. 6 (1968)
25. R. Dönges, Br. Polym. J. 23 (1990) 315–326. 1705–1718.
26. K. G. Rosell,; J. Carbohydr. Chem. 7 (1988) 32. P. W. Arisz, H. T. T. Thai, J. J. Boon, W. G.
525–536. Salomon, Cellulose 3 (1996) 45–61.
27. Henkel & Cie GmbH, GB 754876, 1953. 33. Hercules Powder Company, US 688486, 1950
28. Britisch Celanese Ltd., GB 909039, 1960 (E. (E.D. Dlug, H.G. Tennent).
W. Hitchin, H. Bates). 34. R. W. Butler, E. D. Klug:
29. G. M. Powell: “Hydroxyethylcellulose”, in “Hydroxypropylcellulose”, in Water-Soluble
Water-Soluble Gums Resins, McGraw-Hill, Gums Resins, McGraw-Hill, New York 1980.
New York 1980. 35. Hercules Powder Company, US 3479190,
1969 (A. J. Ganz).