Cellulose Ethers

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

Introduction . . . . . . . . . . . . . . . Properties . . . . . . . . . . . . . . . . . Swelling and Dissolving Behavior . Solution State . . . . . . . . . . . . . . Thermally Induced Coagulation . . Degree of Substitution . . . . . . . . . Molar Mass Distribution . . . . . . . Production . . . . . . . . . . . . . . . . Product Groups . . . . . . . . . . . . . Carboxymethyl Cellulose (CMC) . . Applications / Market . . . . . . . . . . Synthesis . . . . . . . . . . . . . . . . . . Processes . . . . . . . . . . . . . . . . . . Characterization . . . . . . . . . . . . . Methyl and Hydroxyalkyl Methyl Celluloses . . . . . . . . . . . . . . . . . 4.2.1. Applications / Market . . . . . . . . . . 1. 2. 2.1. 2.2. 2.3. 2.4. 2.5. 3. 4. 4.1. 4.1.1. 4.1.2. 4.1.3. 4.1.4. 4.2.

1 1 2 2 4 4 5 5 7 7 7 8 8 8 10 10

4.2.2. 4.2.3. 4.2.4. 4.3. 4.3.1. 4.3.2. 4.3.3. 4.3.4. 4.4. 4.4.1. 4.4.2. 4.4.3. 4.4.4. 5. 6. 7. 8.

Synthesis . . . . . . . . . . . . . . . . . . Processes . . . . . . . . . . . . . . . . . . Characterization . . . . . . . . . . . . . Hydroxyethyl Cellulose (HEC) . . . Applications / Market . . . . . . . . . . Synthesis . . . . . . . . . . . . . . . . . . Processes . . . . . . . . . . . . . . . . . . Characterization . . . . . . . . . . . . . Hydroxypropyl Cellulose (HPC) . . Applications/Market . . . . . . . . . . . Synthesis . . . . . . . . . . . . . . . . . . Processes . . . . . . . . . . . . . . . . . . Characterization . . . . . . . . . . . . . Uses . . . . . . . . . . . . . . . . . . . . . Economic Aspects . . . . . . . . . . . . Toxicology and Occupational Health References . . . . . . . . . . . . . . . . .

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1. Introduction
Cellulose ethers are nontoxic, usually watersoluble, white to yellowish powders or granules. There are some cellulose ethers that are not soluble in water, but their share of sales is insignicant 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 rst published in an article by W. Suida [1] in 1905 and the rst patents [2] relating to their industrial production were issued as early as 1918. In the decade between 1920 and 1930 carboxymethyl cellulose was the rst cellulose ether to gain economic signicance, 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
c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a05 461.pub2

carried out by both industry and academia. Research was and is imperative to enable this group of substances to be utilized in ever new applications. Despite major progress in the areas of regioselective 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 economic signicance. The most important products in terms of sales are carboxymethylcelluloses (approx. 230 000 tons per annum), methyl- and hydroxyalkylmethylcelluloses (approx. 120 000 t/a), hydroxyethylcelluloses (approx. 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 watersoluble, white to yellowish powders or granules.

Cellulose Ethers crystal structure based on hydrogen bridges, the partial imperfection of this structure caused by substituents results in free hydroxyl functions, hence rst the substance becomes soluble in alkalies and subsequently in water. Further etherication with hydrophobic substituents results in solubility in organic solvents and ultimately thermoplasticity (intrinsic solubility). Alongside the hydrophilic-hydrophobic interaction 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 dissolution 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 solution; due to the rising viscosity the mobility within the solution will decrease, leaving undissolved particle residues which will no longer dissolve 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 particle residues preventing formation of a homogeneous solution. To counteract these problems, most suppliers issue recommendations as to which particle size is best for a particular application. Some suppliers also offer specially treated products for enhanced dispersibility. These are mostly powder grades, whose initial dissolving rate is greatly reduced (delayed or retarded solubility) to ensure that the substance is homogeneously distributed in the solvent before starting to dissolve. This delay can be achieved, for instance, by a reversible cross-linkage with glyoxal. The rate of dissolution is thus pH-dependent.

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. The bulk density of cellulose ethers is between 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 inuenced by the degree of substitution. Cellulose ethers are capable of swelling or are colloidally soluble; they increase the viscosity of the solvent and develop a specic rheological prole. Depending on the substitution, cellulose ethers in solution are surface-active (surface tension: water 72 mN/m, carboxymethyl cellulose 70 mN/m, hydroxyethyl cellulose 63 mN/m, methyl cellulose 54 mN/m). The nonionic derivatives are lm-forming substances, resulting in transparent lms with a high elasticity. Solutions and lms obtained from cellulose ethers are compatible with other hydrocolloids. In many applications, however, where certain 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 behavior, the resultant solution structure, and the cellulose ethers 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 specications generally only the degree of purity, the viscosity in aqueous solution 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 interaction between the cellulose ether and the solvent and the intramolecular and intermolecular interaction of the cellulose ether molecules, determines the rheological prole 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

2.1. Swelling and Dissolving Behavior

The different swelling and dissolving behavior of the various cellulose ethers originates from the interplay of the hydrogen bonds between free OH groups on the one hand and hydrophilic and hydrophobic substituent groups on the other. This interplay can be imagined as being the gradual introduction of hydrophobic substituents into native cellulose. Starting from a

Cellulose Ethers (also referred to as Staudinger index) and concentration. All known polymeric solution states from the diluted particle solution to the concentrated network solution [5] can thus be described. However, on account of their inclination 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. Measured in a 2 wt% aqueous solution, it is sometimes included in the product grade designation for orientation purposes. At rst glance this seems to be useful, because many applicationrelated properties are dependent on the same molecular parameters as viscosity. On closer, more discriminating examination, however, this turns out to be misleading, rst 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 viscosity does not describe the solution structure and seldom the products behavior in the nal application system. In the range relevant to the applications the viscosity of cellulose ether solutions rises disproportionately with increasing concentration and intrinsic viscosity:
viscositysolution viscositysolvent (concentration intrinsic viscosity)
3.4 a

(0.5< a < 1.0; a: exponent of the MarkHouwink equation) Most solutions show a pseudoplastic behavior, which is very important in practical terms. Many cellulose ether solutions manifest timedependent rheological functions, so the measurements 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 cellulose 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 ow only starts at stress levels above the so-called yield stress (plastic ow behavior). The intrinsic viscosity describes the volume lled by the free molecule. The intrinsic viscosity is often used as a measure of the molar

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 structure, are also part of the analysis. Many cellulose ethers can be salted out by removing the hydration shell of the molecules. With the ionic products, polyelectrolytic effects such as repulsion 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 actual viscosity achieved by a cellulose ether depends on how well chain scissions can be prevented during the production process and on the type and quantity of substituents introduced into the cellulose molecule. Each substituent represents an increase in molar mass without an increase in the chain length. This reduces the thickening effect. The substituents are, of course, indispensable for solubility and other properties; 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 substituent group with the lowest molar mass is the methyl group which simultaneously cancels out the intermolecular hydrogen bonds very effectively. As pure methyl cellulose manifests a specic temperature-dependent dissolving behavior, which restricts its universal use, mixed cellulose 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 concentration in an aqueous solution has a similarly great effect as that of the chain length. When used as a thickener, the concentration range employed is usually in the range of a moderately concentrated network solution in which the polymer chains are not isolated but looped, forming a temporary physical suspension network. The temperature dependence (below the occulation point) of the ow behavior of aqueous cellulose ether solutions follows the principle

Cellulose Ethers secondary substitution is possible (methyl, carboxymethyl), the molar substitution (MS), i.e., the absolute number of substituents per anhydroglucose unit, is identical to the degree of substitution (DS), i.e., the number of substituents directly linked to the anhydroglucose unit. In the case of substituents containing hydroxyl groups (hydroxyethyl, hydroxypropyl), for example, further (secondary) reactions with the substituent can occur, i.e., there is no decrease in the number of reactive centers. With these products a distinction has to be made between MS and DS. Comparing MS and DS shows the proportion 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 substituent distribution. Primary substitution (i.e., prior to any secondary reactions with the substituent) already involves three kinds of distribution: Substituent distribution within an anhydroglucose 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 borderline cases, which show up the different effects on solubility and therefore on the properties in general. To gain an impression of the distribution along the chain, various breakdown methods and subsequent liquid chromatography or derivatization and gas chromatography 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 fragments 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 individual chains: the substituent density can also

of temperature-time superposition. At a higher temperature all the molecules move faster. If a ow curve (shear stress as a function of the shear rate) is plotted at a reference temperature, the ow curve determined at a higher temperature follows the same shear stress path, except that it is merely shifted to higher shear rates. Accordingly, at the higher temperature the viscosity values are on a lower level. Changes in ow behavior are thus predeterminable (as long as there is sufcient distance from the occulation point). Therefore, when using the cellulose ether as a thickener in aqueous systems, the rheological behavior can be very reliably estimated above and below the reference temperature, if the ow activation energy is known. In the case of many cellulose ethers in aqueous solution the ow activation energy is in the proximity of 40 kJ/mol. Additional substances 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 hydrophobic substituents like methoxy groups decreases as the temperature rises, i.e., the performance of the solvent deteriorates. Cellulose ether dissolved in a cold solution can be made to coagulate 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 occulation point of industrial used products is varied between 30 and 100 C. This is an important characteristic for industrial 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 occulation point with mixed substituent groups, suitable occulation diagrams have been published [7].

2.4. Degree of Substitution

The type of substituent and the degree of substitution determine most of the properties of a cellulose ether. With substituent groups where no

Cellulose Ethers vary between the individual chains of the cellulose ether, one known example being the nonsubstituted cellulose bers in otherwise clear-soluble products. With ionic products the interchain distribution can be detected by polarographic analysis and an appropriate method for other derivatives is chromatography after specically marking the free hydroxyl groups. The problem with both methods 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 adapting the hydrophilic-hydrophobic interaction to suit individual applications increase as well.

into account, some vital assertions can be made relating to existing systems. However, only in rare cases do the results stand up to comparison (between various methods) in respect of an absolute molar mass distribution.

3. Production
Cellulose consists of chains of anhydroglucose units (AGUs) linked together glycosidically (1-4-bonds) ( Cellulose). Accordingly, each AGU still has three free hydroxyl groups which vary in their reactivity and which can be converted to ether groups in polymer-analogous reactions. The free hydroxyl groups form intermolecular and intramolecular hydrogen bonds, so before the cellulose can be etheried 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 sufciently swollen material that is accessible to further reagents. The outcome is known as alkali cellulose or soda cellulose. The degree of swelling is controlled by the ratio of sodium hydroxide 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 cellulose 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 inuence 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 etherication 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 production 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 crucial with regard to the ultimate properties of the cellulose ether. Therefore, many different types

2.5. Molar Mass Distribution

Knowing the molar mass or the molar mass distribution makes it possible in theory to access various material functions. An absolute determination of these variables has so far only been achieved in isolated cases and with an enormous 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. Frequently 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 scattering in many different solvents, and classifying methods such as ultracentrifugation, sizeexclusion chromatography and ow-eld-ow fractionation, and also combined methods involving 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 depend on how the samples have been prepared and how they are inuenced by the measuring procedure itself. Taking the measuring conditions

Cellulose Ethers tanks made handling more difcult and reduced its processability. To make the cellulose more accessible to the chemicals involved, in modern processes the cellulose 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. Alkalization 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 inuence 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 alkalization stage also has a signicant effect on the quality of the cellulose ethers (see above). The reaction can be carried out either batchwise, semibatchwise (fed batch) or continuously, and the reaction temperatures vary from room temperature up to 110 C, depending on the type of etherication. Here again, mixers and stirred vessels are the established equipment. There are some isolated patents describing continuous processes in different equipment setups [14 16]. The starting materials are fed as solids or liquids under pressure. In some older processes for the production of methyl or hydroxyalkylmethyl 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 between 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 includes suction lters, belt lters, drum lters, centrifuges and decanters, operating either continuously 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 washing 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 regenerating the reagents and washing media and for extracting byproducts.

of cellulose obtained from wood pulp or cotton linters are used. The type of cellulose used determines, among others, the maximum chain length, hence the viscosity yield of the nal cellulose ether. The chain length is reduced on account of the chemical and thermal stresses imposed 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, depending on the product category, are used at various 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 cellulose 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 classied by mass fraction into suspension processes (mass fraction below 10 wt%) and slurry processes (mass fraction approx. 10 50 wt%). There is also the option of a gas-phase or vaporphase process, that works without an inert liquid. 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 cellulose 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]. During the ripening process the alkali cellulose was kept in intermediate tanks where the reaction was allowed to complete at a specic temperature. Prior to the ripening stage any excess activating agent was pressed out and the alkali cellulose was then shredded. Storing it in ripening

Cellulose Ethers At the end of the process line the products are converted in forming stages from their brous form into the required supply form, usually powder grades with a dened particle size distribution and containing small amounts of residual 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 elds of application. The particle size distribution ranges from granular grades with an average grain diameter of approx. 0.5 mm to very ne powders where the percentage of particles with a diameter of less than 63 m is higher than 50 wt%.

4. Product Groups
4.1. Carboxymethyl Cellulose (CMC)
In terms of sales volume carboxymethyl celluloses are the largest product group. They are available in various levels of purity from completely unpuried to highly puried for food-grade applications. The CMC group also includes mixed ethers with hydroxyalkyl substituents, that have a predominantly ionic character. 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 puried and another for unpuried CMC. However, the terms puried and unpuried are subject to regional and supplier-

specic differences in denition. Products with an active content of 55 85 % are considered to be unpuried; 85 95 %: semi-puried; around 98 %: puried; and products with an active content greater than 99.5 % are classed as highly puried (high-purity grades). Annual sales worldwide amount to approx. 230 000 t, of which puried CMC accounts for 130 000 t and unpuried CMC totals 100 000 t. It is difcult to accurately apportion gures to the two segments, not only because of varying denitions but also due to the fact that in some applications both puried and unpuried grades of CMC can be used, and many suppliers have both puried and unpuried products in their portfolios. CMC can be produced with less technological input than the other cellulose ethers, which explains why a comparatively large number of manufacturers (more than 20) exists. The leading 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 elds 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 otation aid in drilling mud. Unpuried grades were and in some cases still are used in these applications. Puried products are used in surface coatings and various other technical areas such as in the paper industry for coatings and pulp sizing to improve ber retention, ller/pigment/dye yield as well as strength. CMC also improves the printability and smoothness of paper. Together with gelatin CMC is used as a coacervate to encapsulate ink in the production of noncarbon copy papers. Users of highpurity grades include the cosmetics and pharmaceutical industries, where CMC is used for instance as a fat-free ointment base or as a tablet disintegrant. In food and pet food production CMCs simplest function is to improve consistency and to provide a low-calorie replacement for starch and proteins, or to control more complex functions such as the freeze-thaw stability of deep-frozen products or the creaminess of ice cream.

Cellulose Ethers In contemporary CMC production processes the ground cellulose is processed batchwise either 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 media (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 reaction. Washing with water is not possible because 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 drying 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 waterswellable or alkali-soluble even at a low degree of substitution. The water-solubility of industrially produced CMC begins at a DS of approx. 0.6. The solubility increases up to a rather theoretical DS value of 3.0. Research work has shown that products with a lower degree of substitution (DS < 0.6) can manifest good solubility, 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 simultaneously affect various characteristics. The solution state achieved depends, as with other cellulose ethers, on the nature of the dissolution pro-

4.1.2. Synthesis CMC is produced in a Williamson ether synthesis from alkali cellulose with sodium chloroacetate or with chloroacetic acid itself, which reacts in-situ with caustic soda to form the salt. The process takes place in an aqueous or aqueousalcoholic medium (slurry). The alcohols used are ethanol, isopropanol, tert-butanol and mixtures thereof.
CellOHNaOH+ClCH2 COONa CellOCH2 COONa+NaCl+H2 O

Alkalyzation is carried out at room temperature; the reaction takes place between 50 C and the boiling point of the slurry medium under 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 %. Hydrolysis of chloroacetic acid occurs as a side reaction, forming glycolate. Commercial CMCs are produced with a degree of substitution between 0.2 and 1.5. Carboxymethylation takes place with a slight preference toward C2- followed by C6- and C3-substitution of the anhydroglucose unit [17]. 4.1.3. Processes In the early days of CMC production the cellulose 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 bers, 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, ltered, ground and nally dried. The rst continuous process was used by Wyandotte Chem. Corp. (1947), but there was no washing stage, so it was only suitable for unpuried 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.

Cellulose Ethers

Figure 2. Reaction mixer processes for puried 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 parameter solvent performance covers all thermodynamic effects of protons, salts and other low-molecular substances on the interaction between the solvent and the macromolecule. In addition CMC is a weak carboxylic acid. The proton concentration in the solution not only affects the solvents performance but simultaneously alters the number of free carboxylate groups. CMCs 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 precipitated from the solution at low pH values. Deprotonation increases with rising pH values and the character of the polyelectrolyte becomes apparent: The repulsion among the individual substituents becomes more distinct and the salt sensitivity increases. When CMC comes into contact with selected divalent or trivalent salts, this leads to complexing and in some cases to interlinking and precipitation of the CMC. With divalent salts these effects depend largely on the ratio of substituent to salt [23].

The many different possibilities of microscopic interaction are also reected in the macroscopic properties of CMC. From a rheological point of view CMC solutions are inclined to form superstructures. Viscosities of 2 wt% solutions ranging from 3 mPas to 100 000 mPas are available on the market. Most of the products exhibit pseudoplasticity, some of them a thixotropic behavior. Depending on the selected degree of substitution and the product group, the solutions are either smooth-owing 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 commodities 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.

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Cellulose Ethers low additive contents of between 0.01 and 2 wt% (in relation to the building material system). Accordingly, the cellulose ether has to meet high quality requirements. In the life-science sectors only nonhydroxyalkylated methyl cellulose (modied vegetable gum) and hydroxypropyl methyl cellulose (carbohydrate gum) are used. In the pharmaceutical 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 methylated hydroxypropyl methyl cellulose as a protective colloid in the polymerization of vinyl chloride. 4.2.2. Synthesis

4.2. Methyl and Hydroxyalkyl Methyl Celluloses

Pure methyl cellulose (MC) and hydroxyalkyl methyl celluloses (HAMC) are collectively known as methyl cellulose. Pure methylcellulose only accounts for a minor share of the market. The mixed ethers hydroxyethyl methyl cellulose (HEMC, see Fig. 3) and hydroxypropyl methyl cellulose (HPMC) have established themselves in particular for technical applications.

Figure 3. Structure of HEMC

4.2.1. Applications / Market The market for methyl cellulose and hydroxyalkyl methyl celluloses was in the range of 120 000 t in 2003, the market leader being Dow Chemical Company, with Shin-Etsu Chemical and Wolff Cellulosics having slightly lower market shares. High-purity grades are marketed for applications in the food, pharmaceutical and cosmetics sectors and puried products are used in building materials and industrial applications. The building material segment is by far the largest eld 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 construction methods and traditions ( Dry Mortars). In the USA joint compounds account for the largest segment; in Europe the main applications of MC and HAMC are plasters, renders, and tile adhesives. Efcient modern application methods would not be possible without the use of methyl celluloses. Properties such as water retention, open time, wet adhesion, initial thickening and setting behavior are regulated using only

The synthesis of hydroxyalkyl methyl cellulose is a combination of both principles of synthesis in industrial cellulose ether production: methylation is along the lines of Williamson ether synthesis 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 chloride. In side reactions the methyl chloride is hydrolyzed to form methanol, and subsequently the methanol is etheried by methyl chloride, forming dimethyl ether. The reactions take place between 70 and 120 C. Methylation is an exothermic reaction, the activation energy being 80 kJ/mol.
CellOHNaOH+ClCH3 CellOCH3 +NaCl+H2 O

The grades produced have a degree of substitution 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 cellulose production alkoxylation of the cellulose takes place prior to or parallel to its methylation. As both the cellulose and the alkoxy groups formed can be methylated and alkoxylated, the outcome is a potentially indenite number of

Cellulose Ethers different products, allowing the range of properties to be tailored to the requirements of specic 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 ow is returned to the reactor. The product is then washed, ltered, 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 recent 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 cellulose in any sequence, depending on the targeted product characteristics. The slurry medium has to be added prior to etherication on account of the heat generated during the exothermic reactions. Once the reaction has been completed, low-boiling slurry media are extracted by reducing 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 simple process engineering, whereas disadvantages can be seen in the more complex preparation of the suspension agent. The occulation point of MC and HAMC allows the products to be washed with water above this occulation point. To do so, the contents of the reactor are led into a stirred tank lled with hot water or they are suspended in the reaction mixer; the salts formed during the reaction are

11

dissolved and any nonreacted activation reagents are neutralized with acid. The suspension is then separated in a solid-liquid separating unit. Further washing stages may be required, depending on the product specications, in order to comply reliably with restrictions in content of byproducts. 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 neness of grind, i.e., the particle size, which in some cases is less than 63 m 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 substitution, 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 increasingly hydrophobic. Available on the market are pure methyl celluloses 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 degrees 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 occulation point, because washing with water is less expensive than with alcohol. The occulation point, i.e., the gelation and subsequent coagulation as the temperature rises, is a characteristic found only in nonionic cellulose ethers. By varying the methyl and/or alkyl content of hydroxyalkyl methyl celluloses, it is possible to modify the macromolecules afnity to its water shell and therefore the occulation point: with increasing methyl substitution the number of hydrophilic groups is reduced, and the occulation 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 chloride 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 occulation point shifts to higher temperatures. (The introduction of hydroxypropyl substituents results in opposite characteristics where, depending on the degree of substitution, the occulation point either rises or drops.) Especially for applications where there is a high ambient temperature, e.g. on building sites in the summer, a methyl cellulose (MHEC or MHPC) with a sufciently high occulation point should be used to eliminate any undesired changes in characteristics. The rheological properties of methyl celluloses and hydroxyalkyl methyl celluloses vary within a broad range, exhibiting some very different features, because there is a wide viscosity range in the grade spectrum available and because the products can have very differing chemical structures. Products with a particularly low viscosity, such as HPMC for tablet coatings with a typical viscosity of between 3 and 6 mPas at a concentration of 2 wt% in water, still show a purely Newtonian (ideal) ow behavior in aqueous solutions with a HPMC concentration of 10 20 wt% at room temperature, and the viscosity of these solutions can be as high as 10 000 mPas. The Newtonian behavior is crucial for

spraying highly concentrated solutions and for good leveling and lm formation. HEMC or HPMC grades with a higher viscosity for use as thickeners, however, exhibit a non-Newtonian ow behavior even with at low concentrations. In building materials applications, such as tile adhesives, the high static shear viscosity guarantees standing strength and resistance to demixing as well as high water retention, while the non-Newtonian properties ensure 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 cementbased building materials in which, after water is added, highly alkaline conditions prevail. The most effective way to achieve good thickening at a low shear rate is to use small input quantities of high-viscosity grades. In these systems 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 benets, such as

Cellulose Ethers long open times and improved adhesion in the case of tile adhesives.

13

4.3. Hydroxyethyl Cellulose (HEC) [29]

Hydroxyethyl celluloses are the third largest product group in the marketplace. They are nonionic and soluble in both cold and hot water. Their manufacture was rst described in 1920 in a patent granted to Farbenfabriken Bayer. The structure of HEC is shown in Figure 5.

hydrophobically modied grades are, like purely synthetic associative thickeners, capable of providing additional effects by interacting with particle 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 leveling. 4.3.2. Synthesis Hydroxyethyl cellulose is formed by reaction of cellulose with ethylene oxide. This ethoxylation only requires catalytic quantities of alkaline solution.
CellOH+OH CellO +H2 O CellO +CH2 CH2 OCellOCH2 CH2 O CellOCH2 CH2 O +H2 O CellOCH2 CH2 OH+OH

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 specically in surface coatings. Hydroxyethyl cellulose is also found in cosmetic applications where it competes against HPMC derivatives. Other applications are in drilling uids 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 rmly established in these applications for technical and cost-related reasons. Beside pure HEC this product group also includes mixed cellulose ethers similar to HEC: ethyl hydroxyethyl cellulose (EHEC) and hydrophobically modied (hm) variants of HEC. The additional hydrophobic properties are imparted to hm-HEC by minor secondary substitution, for instance with longchain alkyl residues (C12 through C24 ) [30]. The

Just as the cellulose alcoholate reacts with the ethylene oxide, also the hydroxyl ions present can react with the ethylene oxide or with the glycolates formed in the process. Large amounts of alkali reduce the yield of the main reaction, but to produce HEC a minimum quantity of caustic 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 being controlled via the quantity of ethylene oxide added. The yield is between 40 and 75 % in relation to ethylene oxide. The reaction of ethylene oxide takes place in the following order of preference (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 inuenced by varying the alkali concentration, e.g., by partial neutralization [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 ltration process; j) Stream dryer; k) Comminuting; l) Screening equipment; m) Slurry medium recycling

4.3.3. Processes For the production of HEC, suspension processes above ambient pressure have become the established methods [33]. Stirred pressure vessels are used for the reaction (see Fig. 6). The ground cellulose is suspended in the suspending 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 occulation 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 selected for this.

4.3.4. Characterization Hydroxyethyl celluloses are available on the market with viscosities between 10 mPas and 100 000 mPas and molar substitutions of 1.5 and 3.0 (up to 4.5 in the case of hydrophobically modied grades). They are water-soluble and have no thermal occulation point. Hydroxyethyl celluloses are also more difcult to salt out than methylated derivatives and are not displaced from water even by larger amounts of organic solvent. The degree of substitution varies in the region of 1 in industrially produced grades, i.e., higher hydroxyethylation leads chiey to secondary, tertiary, and quaternary substitution of the hydroxyalkyl substituent (formation of ethylene oxide side chains). The rheological behavior of HECs is comparable with that of carboxymethyl celluloses. By introducing a small number of hydrophobic side chains, grades can be obtained, whose rheological prole in solution is highly modied,

Cellulose Ethers particularly when mixed with surfactants. The hydrophobic residues form part of the surfactant micelles and this increases the viscosity, especially at elevated shear rates.

15

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 solubility in cold water to enhanced thermoplasticity, which enables them to be processed in melt extruders. Hydroxypropyl cellulose was rst launched on the market in the USA at the end of the 1960s. The structure of hydroxypropyl cellulose is shown in Figure 7.

cellulose is activated with caustic soda solution. The reaction has a somewhat higher activation energy and requires a higher reaction temperature than that with ethylene oxide. The byproducts are propylene glycol and polypropylene glycols which, like the salts from the neutralization 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 generally carried out in a slurry. The slurry media described in relevant literature are hexane, toluene, tetrahydrofuran and dioxane, and also the common alcohols. Apart from the slurry process, the gas-phase method which produces highquality grades due to the high degree of substitution is also applied. Since highly substituted HPC has a thermal occulation point, however, washing can be carried out using hot water, which is not possible with HEC [35]. 4.4.4. Characterization

Figure 7. Structure of HPC

4.4.1. Applications/Market The annual global market for hydroxypropyl cellulose is far below 10 000 t. The main elds of application are in the pharmaceutical and cosmetics industries [34]. High-purity grades are available for food and pharmaceutical applications, and puried grades are supplied to the cosmetics 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

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 mPas. HPC solutions are generally smoothowing and exhibit scarcely any tendency toward thixotropic behavior. Gelation and coagulation begins at relatively low temperatures (40 50 C). Hydroxypropyl cellulose is surfaceactive and tends to foam. Highly concentrated HPC solutions can develop liquid-crystalline phases. With a sufciently high degree of substitution hydroxypropyl cellulose is thermoplastic and can be processed at approx. 150 C. The extruded 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 between 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 manufacture of tablets.

16

Cellulose Ethers followed by hydroxyethylcelluloses on third place with approx. 60 000 t/a and last by hydroxypropylcellulose with less than 10 000 t/a. Taking all market segments together, the cellulose 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 number of suppliers of cellulose derivatives. Most of the manufacturers produce a variety of different 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 Company, Wolff Cellulosics, and Shin-Etsu Chemical (incl. SE Tylose, the former cellulose ether division of Clariant AG)] with a market share totaling 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.

5. Uses
Cellulose ethers are used in a wide variety of elds ranging from oil drilling to industrial applications such as polymerization, from surface coatings and construction materials to the health care sector, cosmetics, food and pharmaceuticals. Not all types of cellulose ethers are equally suitable in all elds of application. Table 1 provides an overview of the great variety of applications and the appropriate types of cellulose ether. A listing of this kind can only be incomplete, but indicates the versatility and above all the adaptability of the products to the various elds 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, lm formation and thickening as well as for controlling other rheological properties. Many modern products and processing techniques would not be possible without the use of cellulose ethers. Each eld of application requires specic solutions which in many cases involve modifying the cellulose ether product. This means that, once a suitable product category has been selected, all the parameters relating to the appropriate type of substitution and viscosity range have to be ne-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 experience in respect of the properties of these products as well as with regard to the systems and methods of application. Most suppliers provide this expertise and offer additional technical service.

7. Toxicology and Occupational Health

Toxicology. Cellulose ethers are generally nontoxic. High-purity grades of most commercial 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 polysaccharides or sawdust. Dry nonionic ethers undergo 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 ammability is similar to that of cellulose. Spilling of solutions forms very slippery lms that are difcult 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

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 signicance (by sales volume), carboxymethylcelluloses rank rst with approx. 230 000 t/a, while methyl- and hydroxyalkylmethylcelluloses are second with approx. 120 000 t/a,

Cellulose Ethers
Table 1. Major elds of application in which the individual product groups are used Carboxymethyl cellulose Paper Detergents Drilling for oil and gas Pharma Cosmetics Textile industry Food Coatings Encapsulation Methyl cellulose, hydroxyalkyl methyl cellulose tile adhesives plasters/renders pharma/cosmetics joint compounds wallpaper paste polymerization food latex paints cement extrusion Hydroxyethyl cellulose latex paints adhesives building materials cosmetics drilling for oil & gas agriculture paper synthetic resins textile industry Hydroxypropyl cellulose adhesives ceramics cosmetics

17

encapsulation food household goods printing inks polymerization lms

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 sh toxicity and are poor nutrients for most microorganisms. Nevertheless, wastewater bacteria may adapt to enhanced 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
1. W. Suida, Monatshefte Chemie 26 (1905) 413427. 2. E. Jansen, DE 332203, 1918. 3. D. Klemm, et al.: Comprehensive Cellulose Chemistry, Vol. 2, WILEY-VCH Verlag GmbH, Weinheim 1998. 4. J. Schurz, et al.: Methodische Fortschritte in der Instrumentalanalytik, Das Papier 12 (1999) 712764. 5. W. W. Graessley, Polymer 21 (1980) 258. 6. W.-M. Kulicke, et al.: Characterization of aqueous carboxymethylcellulose solutions in terms of their molecular structure and its inuence on rheological behaviour, Polymer 37/13 (1996) 27232731. 7. R. D nges, Das Papier 12 (1997) 653670. o 8. P. K uper, et al.: Development and evaluation a of methods for determining the pattern of functionalization in sodium carboxymethylcelluloses, Angew. Makromol. Chem. 260 (1998) 5363. 9. P. Mischnick, et al.: Structure Analysis of 1,4-Glucan Derivatives, Macromol. Chem. Phys. 201 (2000) 19851995.

10. P. W. Arisz: Substituent distribution along the cellulose backbone in O-methylcelluloses using GC and FAB-MS for monomer and oligomer analyses, Carbohydr. Res. 271 (1995) 114. 11. B. Reiche, H. Jehring, H. Dautzenberg, B. Philipp: Elektrosorptionsuntersuchungen an Carboxymethylcellulosen, Faserforschung und Textiltechnik 29/5 (1978) 324328. 12. Cellulose, in: Ullmann, 6th ed., vol. 6, WILEY-VCH Verlag GmbH, Weinheim 2002, pp. 593645. 13. O. Wurz: Cellulose ther - Herstellung und a Anwendung, Roether, Darmstadt 1961. 14. Kalle AG, DE 1543136, 1969 (F, Eichenseer, S. Janocha, H. Macholdt ). 15. Dow Chemical Company, US 4015067, 1975 (G.Y.T Liu, C.P. Stange). 16. Henkel KgaA, DE 2929011, 1981 (W. Willi, H. Leischner, W. R hse, F.-J. Carduck, N. a K hne). u 17. H. M. Spurlin, J. Am. Chem. Soc. 61 (1939) 2222. 18. J. Voss: Cellulose ther, in a Kunststoffhandbuch, vol. 3, Hanser, M nchen u 1965 pp. 349397. 19. R. N. Halder, W. F. Waldeck. F. W. Smith, Ind. Eng. Chem. 44 (1952) 2803. 20. V. Stigsson, G. Kloow, U. Germg rd, a PaperAsia 17/10 (2001) 1621. 21. R. D nges, Das Papier 12 (1997) 653670. o 22. T. Heinze, T. Liebert, P. Kl fers, F. Meister: u Carboxymethylation of cellulose in unconventional media, Cellulose 6 (1999) 153165. 23. P. K uper: Natriumcarboxymethylcellulose: a Bestimmung der chemischen Struktur, der L sungsstruktur und der o Elektrolytwechselwirkungen, Berichte aus der Chemie (1998), Shaker, Aachen.

18

Cellulose Ethers
30. L.-M. Zhang, Carbohydr. Polym. 45 (2001) 110. 31. M. G. Wirick, J. Polym. Sci. 6 (1968) 17051718. 32. P. W. Arisz, H. T. T. Thai, J. J. Boon, W. G. Salomon, Cellulose 3 (1996) 4561. 33. Hercules Powder Company, US 688486, 1950 (E.D. Dlug, H.G. Tennent). 34. R. W. Butler, E. D. Klug: Hydroxypropylcellulose, in Water-Soluble Gums Resins, McGraw-Hill, New York 1980. 35. Hercules Powder Company, US 3479190, 1969 (A. J. Ganz).

24. Dry Mortars, in: Ullmann, 6th ed., vol. 11, WILEY-VCH Verlag GmbH, Weinheim 2002, pp. 83108.. 25. R. D nges, Br. Polym. J. 23 (1990) 315326. o 26. K. G. Rosell,; J. Carbohydr. Chem. 7 (1988) 525536. 27. Henkel & Cie GmbH, GB 754876, 1953. 28. Britisch Celanese Ltd., GB 909039, 1960 (E. W. Hitchin, H. Bates). 29. G. M. Powell: Hydroxyethylcellulose, in Water-Soluble Gums Resins, McGraw-Hill, New York 1980.