CELLULOSE ETHERS

1. General Considerations

Alkylation of cellulose yields a class of polymers generally termed celluloseethers. Most of the commercially important ethers are water-soluble and arekey adjuvants in many water-based formulations. The most important propertythese polymers provide to formulations is rheology control, ie, thickening andmodulation of flow behavior. Other useful properties include water-binding (absorbency, retention), colloid and suspension stabilization, film formation,lubrication, and gelation. As a result of these properties, cellulose ethers havepermeated a broad range of industries including foods, coatings, oil recovery, cos-metics, personal care products, pharmaceuticals, adhesives, printing, ceramics,textiles, building materials, paper, and agriculture.Estimates from SRI International figures indicate that the world consump-tion, excluding eastern European countries and the former Soviet Union, of allgrades of cellulose ethers in 1987 was about 230,000 t (1). Cellulose ethers repre-sent a mature industry with annual sales of over one billion dollars and annualgrowth rate averaging 2–3% per year. The U.S. consumption in 1987 wasapproximately 69,000 t, Western Europe about 116,000 t, and Japan about22,000 t. Prices for the principal products range from about $1.65/kg for crudegrades of sodium carboxymethylcellulose to over $11/kg for purified hydroxypro-pylcellulose. The highest volume cellulose ethers, the industry workhorses, aresodium carboxymethylcellulose, hydroxyethylcellulose, and hydroxypropyl-methylcellulose. Cellulose ethers as a class compete with a host of other materi-als including natural gums, starches, proteins (qv), synthetic polymers, and eveninorganic clays (see C

ARBOHYDRATES

; G

UMS

). They provide effective performance atreasonable cost and are derived from a renewable, natural resource.Cellulose ethers are manufactured by reaction of purified cellulose withalkylating reagents under heterogeneous conditions, usually in the presence of a base, typically sodium hydroxide, and an inert diluent. Cottonseed linterfiber and wood fiber are the principal sources for cellulose. Purified cellulosecotton linters, commonly termed chemical cottons, are generally of higher purityand higher maximum molecular weight than purified cellulose from dissolving grades of wood pulp. The base, in combination with water, activates the cellulosematrix by disrupting hydrogen-bonded crystalline domains, thereby increasing accessibility to the alkylating reagent. This activated matrix is commonly termedalkali cellulose (2–6). The base also promotes the etherification reaction. Theseveral purposes of the inert diluent are to suspend/disperse the cellulose,provide heat transfer, moderate reaction kinetics, and facilitate recovery of theproduct. Crude grades of cellulose ethers, most notably sodium carboxymethyl-cellulose, may be made in the absence of any diluent. Reactions are typicallyconducted at elevated temperature,

50 to 140

C, and under nitrogen to inhibitoxidative molecular weight degradation of the polymer (7,8), if so desired. Afterreaction, crude grades are simply dried, ground, and packed out; puriﬁed gradesrequire removal of byproducts in a separate operation prior to drying. Variousadditives, such as colloidal silicas, may be added in small amounts to some

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Kirk-Othmer Encyclopedia of Chemical Technology

products prior to drying or before packout to improve dry handling properties. Inaddition to these unit operations, schematically outlined in Figure 1, a molecularweight reduction operation may be included in the process at any of severalpoints, most notably either in the reaction vessel (before, during, or after thealkylation reaction), after puriﬁcation before drying, or treatment of dry material(9–11). Hydrogen peroxide is commonly used, though deliberate degradationmay also be induced through controlled alkaline-catalyzed autoxidation withoxygen (air) in the reactor. Acids can also be used to cleave the cellulose chain(12,13). An important characterization parameter for cellulose ethers, in addition tothe chemical nature of the substituent, is the extent of substitution. As theHaworth representation of the cellulose polymer shows, it is a linear, unbranchedpolysaccharide composed of glucopyranose (anhydroglucose) monosaccharideunits linked through their 1,4 positions by the

anomeric conﬁguration.

OHOHHCH

OHHOHHOHHOOCH

OHHHHOHOHOHCH

OHHOHHHOOCH

OHHHOHHOHHOHHHOHHOH

453 21 43 21656

The structurally similar starch amylose polymer is linked through the

anom-eric conﬁguration. The three hydroxyl functions per anhydroglucose unit arenoteworthy; these hydroxyls are the active sites for ether formation.The extent of substitution is described as the degree of substitution (DS),deﬁned as the average number of hydroxyl groups substituted per anhydroglu-cose unit. Excluding the terminal residues, each anhydroglucose moiety hasthree available hydroxyl groups for a maximum DS value of three. In certain

Reaction PurificationBy-products,organic diluent,waterCelluloseSodium hydroxideWaterOrganic diluentAlkylating reagent(s)Drying Grinding PackoutAqueous diluents or waterOrganic diluent,water

Fig. 1.

Unit operations for the manufacture of puriﬁed cellulose ethers.

446 CELLULOSE ETHERS Vol. 5

cases the alkylating reagent, such as an alkylene oxide, generates a new hydro-xyl group upon reacting which can then further react to give oligomeric chains.The product is then characterized by its molar substitution (MS), the moles of reagent combined per mole of anhydroglucose unit. The ratio of MS to DS is ameasure of the average chain length of the oligomeric side chains. Organo-soluble ethylcellulose has a DS of 2.3–2.8. Most water-soluble derivatives haveDS values of 0.4–2.0. Hydroxyalkyl ethers have MS values typically between 1.5and 4.0.MS and DS values are average values, placing no signiﬁcance on the formaldistribution of the substituents within or among polymer chains. Substituent dis-tribution, however, is an important molecular parameter affecting solution rheol-ogy and ultimately end use properties. A classic example is offered by sodiumcarboxymethylcellulose (14). Depending on reaction conditions, sodium carboxy-methylcellulose (CMC) of DS

80 can be made to exhibit a varying degree of solution thixotropy, the effect being dependent not so much on degree of substi-tution but rather on the distribution of substituents.Thixotropic solutions are characterized by a decrease in viscosity on shear-ing followed by a time-dependent increase after the shear stress is removed. A plot of shear rate versus shear stress reveals a hysteresis loop. Associationamong polymer chains via electrostatic, hydrogen-bonding, or hydrophobiceffects can lead to thixotropy. Carboxymethyl substituent uniformity along thepolymer chain affects thixotropic behavior of CMC because regions of contiguousunsubstituted anhydroglucose units, ie, blocks, among polymer chains tend toassociate through hydrogen bonding (15). The extent of blockiness is controlledby reaction conditions. Solution thixotropy is important in applications requiring suspension or stabilization of particulates. As substituent uniformity is increased, either by choosing appropriate reac-tion conditions or by reaction to high degrees of substitution, thixotropic beha-vior decreases. CMCs of DS

0 generally exhibit pseudoplastic rather thanthixotropic rheology. Pseudoplastic solutions also decrease in viscosity undershear but recover instantaneously after the shear stress is removed. A plot of shear rate versus shear stress does not show a hysteresis loop.Other examples illustrating the effect of substituent distribution on proper-ties include: (

) enzymatic stability of hydroxyethylcellulose (16,17); (

) salt com-patibility of carboxymethylcellulose (18,19); and (

) thermal gelation propertiesof methylcellulose (20). The enzymatic stability of hydroxyethylcellulose is anexample where the actual position of the substituents within the anhydroglucoseunits is considered important. Increasing substitution at the C2 position pro-motes better resistance toward enzymatic cleavage of the polymer chain.Positional distribution is also a factor in the other two examples.

C-nmr is the premier method for the compositional and structural charac-terization of cellulose ethers (21–27). Another analytical method is based onchromatography of hydrolyzates (28). The results show that the reactivity of the three hydroxyl groups can vary signiﬁcantly depending on the alkylating reagent, the type of reaction, and reaction conditions. For most cellulose ethers,substitution occurs primarily at the C2 and C6 hydroxyl groups (29). Aside from the chemical nature of the substituent and its DS (MS) and dis-tribution, solution viscosity, ie, polymer molecular weight, is another important