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Carboxymethyl cellulose
Carboxymethyl cellulose
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Carboxymethyl cellulose
Names
Other names
Carboxymethylcellulose; carmellose; E466
Identifiers
ChEBI
ChEMBL
ChemSpider
  • none
ECHA InfoCard 100.120.377 Edit this at Wikidata
E number E466 (thickeners, ...)
UNII
Properties
variable
Molar mass variable
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Carboxymethyl cellulose (CMC) or cellulose gum[1] is a cellulose derivative with carboxymethyl groups (-CH2-COOH) bound to some of the hydroxyl groups of the glucopyranose monomers that make up the cellulose backbone. It is often used in its sodium salt form, sodium carboxymethyl cellulose. The addition of carboxylic acid groups to the cellulose backbone allows carboxymethyl cellulose to be dissolved in water unlike natural cellulose. This allows its use in numerous food and pharmaceutical applications that require water-soluble polymers.

Preparation

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Carboxymethyl cellulose is synthesized by the alkali-catalyzed reaction of cellulose with chloroacetic acid.[2][3] The polar (organic acid) carboxyl groups render the cellulose soluble and chemically reactive.[4] Fabrics made of cellulose – e.g., cotton or viscose (rayon) – may also be converted into CMC.[5]

Following the initial reaction, the resultant mixture produces approximately 60% CMC and 40% salts (sodium chloride and sodium glycolate). This product, called technical CMC, is used in detergents, where it is used as a thickening agent.[6][7] An additional purification process is used to remove salts to produce pure CMC, which is used for food and pharmaceutical applications.[8] An intermediate 'semi-purified' grade is also produced, which is typically used in paper applications such as the restoration of archival documents.[9]

Structure and properties

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Structure

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CMC is a derivative of the regenerated cellulose [C6H10O5]n with hydroxy-acetic acid (hydroxyethanoic acid) CH2(OH)COOH or sodium monochloroacetate (Na[ClCH2COO]). The CMC backbone consists of D-glucose residues linked by -1,4-linkage. It has carboxymethyl groups (-CH2-COOH) bound to some of the hydroxyl groups of the glucopyranose monomers that make up the cellulose backbone. It is often used as its sodium salt, sodium carboxymethyl cellulose.[10]

Properties

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CMC is a white or lightly yellow powder with no odor, flavor, or poisonous properties. It is hygroscopic and dissolves well in hot or cold water, forming a viscous solution. It is not soluble in organic solvents like methanol, ethanol, acetone, chloroform, and benzene. The functional properties of CMC depend on the degree of substitution of the cellulose structure (i.e., how many of the hydroxyl groups have been converted to carboxymethylene groups in the substitution reaction), as well as the chain length of the cellulose backbone structure and the degree of clustering of the carboxymethyl substituents. It is commonly used as a viscosity modifier or thickener and to stabilize emulsions in various products, both food and non-food-related. It is mainly used because it has a high viscosity, is nontoxic, and is generally considered to be hypoallergenic.

Uses

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Carboxymethyl cellulose (CMC) is used in applications ranging from food production to medical treatments.[11][10] It is commonly used as a viscosity modifier or thickener and to stabilize emulsions in both food and non-food products. It is used primarily because it has high viscosity, is nontoxic, and is generally considered to be hypoallergenic, as the major source fiber is either softwood pulp or cotton linter. It is also used in non-food products which include products such as toothpaste, laxatives, diet pills, water-based paints, detergents, textile sizing, reusable heat packs, various paper products, filtration materials, synthetic membranes, wound healing applications, and also in leather crafting to help burnish edges.[12][13][14][verification needed]

Food

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CMC is registered as E466 or E469 (when it is enzymatically hydrolyzed). It is used for a viscosity modifier or thickener and to stabilize emulsions in various products, including ice cream, mayonnaise, and beverages. It is also used extensively in gluten-free and reduced-fat food products.[15] CMC injections have also been used in food fraud, to fraudulently increase the weight and visual appeal of shrimp and prawns so as to short-weight customers.[16]

CMC's variable viscosity (high while cold, and low while hot) makes it useful in the preparation of cold foods and textures in beverages and edible gels. With a degree of substitution (DS) around 1.0, it can prevent dehydration and shrinkage of gelatin while also contributing to a more airy structure. In some foods, it can be used to control oil and moisture content.[17]

CMC is used to achieve tartrate or cold stability in wine, which can prevent excess energy usage while chilling wine in warm climates. It is more stable than metatartaric acid and inhibits tartrate crystal nucleation and growth.[18][19][20]

CMC powder is widely used in the ice cream industry to make ice creams without the need for churning or extremely low temperatures.[21] CMC is used in baking breads and cakes. The use of CMC gives the loaf an improved quality (e.g., texture) at a reduced cost by reducing the need for fat. CMC is also used as an emulsifier in sweet biscuits. Dispersing fat uniformly in the dough improves the release of the dough from the molds and cutters, achieving well-shaped biscuits without any distorted edges. It can also help to reduce the amount of egg yolk or fat used in making the biscuits. The use of CMC in candy preparation ensures smooth dispersion in flavor oils and improves texture and quality. CMC is used in chewing gums, margarine, and peanut butter as an emulsifier.[22]

Detergent uses

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CMC is a common ingredient in cleaning products because of its thickening and stabilizing properties and nontoxic composition. In detergent and cleaning products, it can be used to enhance texture and assist in the suspension of dirt and grime in the cleaning product. Its adjustable viscosity can be used to standardize the textures of the products, especially when used along with other chemicals.[7][6]

CMC helps with the removal of grease and aids in the creation of small bubbles in the soap. This, along with its ability to suspend dirt in mixtures, can make soaps and other cleaning products more efficient.[23]

Textile uses

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CMC is used in textiles as a thickening agent in textile printing, constituting about 2-3% of printing pastes. It is also used in fabric finishing to affect the fabric's texture. Additionally, CMC serves as a binding agent in non-woven fabrics, contributing to the strength and stability of the material. In sizing applications, about 1-3% of CMC is used to protect yarns during weaving to reduce breakages.

CMC aids in thickening printing pastes, which makes the prints themselves more precise. It is also used to thicken dyes. Additionally, it is an alternative to synthetic thickeners.[24]

Cosmetics uses

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CMC is an ingredient used in over 50% of cosmetic products. As a thickening agent, it is used in formulations where viscosity needs to be precisely controlled. In hair care, about 25% of shampoos and conditioners utilize CMC for its conditioning and detangling effects. It is also used in the makeup and toothpaste industries to control the products' texture. Due to its ability to retain moisture, it is also used in skincare products. CMC serves as a film-forming agent in approximately 10% of sunscreens.

CMC aids in pigment suspension and dispersion, binding other ingredients for even distribution. CMC, when combined with Fatty Acid Ethanolamine or 2,2'-Iminodiethanol in a hair product, can form a thin film around the hair.[25]

Oil Drilling

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As a thickening agent, CMC can increase the viscosity of drilling fluids and form a network structure in the mud, thereby enhancing their suspension capacity. CMC can effectively protect the wellbore and manage the penetration and loss of moisture in the drilling fluid. Ultra-high viscosity Sodium Carboxymethyl Cellulose can be used in fracturing fluids, primarily to carry fillers into oil wells.[26]

Medical applications

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CMC is also used in numerous medical applications.[11][14][27][28]

Some examples include:

  • Device for epistaxis (nose bleeding). A poly-vinyl chloride (PVC) balloon is covered by CMC knitted fabric reinforced by nylon. The device is soaked in water to form a gel, which is inserted into the nose of the patient and inflated. The combination of the inflated balloon and the therapeutic effect of the CMC stops the bleeding.[29]
  • Hydrofiber fabric used as a medical dressing following ear, nose, and throat surgical procedures.[30]
  • Water is added to form a gel, and this gel is inserted into the sinus cavity following surgery.[31]
  • In ophthalmology, CMC is used as a lubricating agent in artificial tears solutions for the treatment of dry eyes.[32]
  • In veterinary medicine, CMC is used in abdominal surgeries in large animals, particularly horses, to prevent the formation of bowel adhesions.[33]

Research applications

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Insoluble CMC (water-insoluble) can be used in the purification of proteins, particularly in the form of charged filtration membranes or as granules in cation-exchange resins for ion-exchange chromatography.[34] Its low solubility is a result of a lower DS value (the number of carboxymethyl groups per anhydroglucose unit in the cellulose chain) compared to soluble CMC.[35] Insoluble CMC offers physical properties similar to insoluble cellulose, while the negatively charged carboxylate groups allow it to bind to positively charged proteins.[36] Insoluble CMC can also be chemically cross-linked to enhance the mechanical strength of the material.[37]

Moreover, CMC has been used extensively to characterize enzyme activity from endoglucanases (part of the cellulase complex); it is a highly specific substrate for endo-acting cellulases, as its structure has been engineered to decrystallize cellulose and create amorphous sites that are ideal for endoglucanase action.[citation needed] CMC is desirable because the catalysis product (glucose) is easily measured using a reducing sugar assay, such as 3,5-dinitrosalicylic acid.[citation needed] Using CMC in enzyme assays is especially important in screening for cellulase enzymes that are needed for more efficient cellulosic ethanol conversion.[citation needed] CMC was misused in early work with cellulase enzymes, as many had associated whole cellulase activity with CMC hydrolysis.[according to whom?] As the mechanism of cellulose depolymerization became better understood, it became clear that exo-cellulases are dominant in the degradation of crystalline (e.g. Avicel) and not soluble (e.g. CMC) cellulose.[citation needed]

Other uses

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In laundry detergents, it is used as a soil suspension polymer designed to deposit onto cotton and other cellulosic fabrics, creating a negatively charged barrier to soils in the wash solution.[citation needed] CMC is also used as a thickening agent, for example, in the oil-drilling industry as an ingredient of drilling mud, where it acts as a viscosity modifier and water retention agent.[citation needed]

CMC is sometimes used as an electrode binder in advanced battery applications (i.e. lithium ion batteries), especially with graphite anodes.[38] CMC's water solubility allows for less toxic and costly processing than with non-water-soluble binders, like the traditional polyvinylidene fluoride (PVDF), which requires toxic n-methylpyrrolidone (NMP) for processing.[citation needed] CMC is often used in conjunction with styrene-butadiene rubber (SBR) for electrodes requiring extra flexibility, e.g. for use with silicon-containing anodes.[39]

CMC is also used in ice packs to form a eutectic mixture resulting in a lower freezing point, and therefore more cooling capacity than ice.[40]

Aqueous solutions of CMC have also been used to disperse carbon nanotubes, where the long CMC molecules are thought to wrap around the nanotubes, allowing them to be dispersed in water.[citation needed]

In conservation-restoration, it is used as an adhesive or fixative (commercial name Walocel, Klucel).[citation needed]

Adverse reactions

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Effects on inflammation, microbiota-related metabolic syndrome, and colitis are a subject of research.[41] Carboxymethyl cellulose, along with other emulsifiers, is suggested as a possible cause of inflammation of the gut,[42] through alteration of the human gastrointestinal microbiota, and has been suggested as a triggering factor in inflammatory bowel diseases such as ulcerative colitis and Crohn's disease.[43][44] A small randomized human study found that consumption of high amounts of CMC altered gut microbiota composition and was associated with increased gastrointestinal discomfort. [45]

While thought to be uncommon, case reports of severe reactions to CMC exist.[46] Skin testing is believed to be a useful diagnostic tool for this purpose.[47]

See also

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References

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Revisions and contributorsEdit on WikipediaRead on Wikipedia
from Grokipedia
Carboxymethyl cellulose (CMC), often encountered as its sodium salt sodium carboxymethylcellulose, is a water-soluble anionic polysaccharide derived from cellulose through the chemical modification of its hydroxyl groups with carboxymethyl (-CH₂COOH) substituents via an alkali-catalyzed reaction with chloroacetic acid. This derivative, with the CAS number 9004-32-4 and a representative molecular formula of [C₆H₇O₂(OH)₃₋ₓ(OCH₂COONa)ₓ]ₙ for the sodium salt, forms highly viscous colloidal solutions in water, making it a key ingredient in numerous applications. CMC exhibits excellent thickening, stabilizing, and emulsifying properties due to its polyelectrolyte nature and ability to form gels or viscous fluids depending on concentration, pH, and degree of substitution (typically 0.6–1.2). It is odorless, tasteless, and biodegradable, with solubility in cold and hot water but insolubility in most organic solvents, rendering it ideal for aqueous-based formulations. These characteristics stem from its linear chain structure, where the carboxymethyl groups enhance hydrophilicity and ionic interactions. In the food industry, CMC serves as a viscosity modifier to improve texture, prevent syneresis in products like ice cream and yogurt, and stabilize emulsions in salad dressings and beverages, often approved as a safe additive (E466 in the EU). Pharmaceutically, it functions as a bulk-forming laxative, a suspending agent in oral liquids, and a binder in tablets, leveraging its non-toxic and hypoallergenic profile. Beyond these, CMC finds use in cosmetics as a thickener in lotions, in detergents for soil suspension, and in industrial applications such as paper coatings and oil drilling fluids for rheology control.

Introduction

Definition and general characteristics

Carboxymethyl cellulose (CMC), also known as sodium carboxymethyl cellulose, is the sodium salt of a carboxymethyl ether of cellulose, serving as an anionic water-soluble polymer derived from natural cellulose sources such as wood pulp or cotton linters. This semi-synthetic derivative modifies the hydroxyl groups of cellulose, the most abundant natural polysaccharide, through carboxymethylation to enhance its solubility and functionality. CMC typically exhibits a high molecular weight ranging from 90,000 to 1,200,000 Da, appearing as a white to off-white, hygroscopic powder that is odorless and tasteless. When dissolved in water, it forms clear, viscous colloidal solutions whose thickness increases with concentration, enabling its role as a thickening, stabilizing, and suspending agent in various formulations. As a semi-synthetic polysaccharide, CMC is biodegradable under aerobic conditions, such as in activated sludge environments, and is recognized for its non-toxicity and broad compatibility with other substances, making it suitable for diverse industrial applications including food and pharmaceuticals. Its general repeating unit structure is represented as [\ceC6H7O2(OH)3x(CH2COONa)x]n[ \ce{C6H7O2(OH)_{3-x}(CH2COONa)_x} ]_n, where xx denotes the degree of substitution (DS), typically ranging from 0.4 to 1.5, which influences its solubility and viscosity properties.

Historical development

Carboxymethyl cellulose (CMC) was first synthesized in 1918 by German chemist Erich Jansen through etherification of cellulose, aiming to create a water-soluble derivative as a substitute for scarce natural gums like guar and locust bean gum during post-World War I shortages. This innovation addressed the need for affordable, versatile thickeners in industrial applications, marking the initial step toward commercial viability. Early experiments focused on reacting cellulose with chloroacetic acid under alkaline conditions, yielding a product with enhanced solubility and stability compared to unmodified cellulose. Commercialization accelerated in the 1930s, with companies such as Hercules Powder Company (later Ashland Inc.) introducing CMC to markets for its utility as a stabilizer and binder. Initial patents, including one granted in 1921 to early developers, targeted applications in textiles for warp sizing and in paper production for improved surface properties and retention. By the late 1930s, production scaled up in the United States and Europe, driven by demand in sectors requiring non-toxic, water-dispersible polymers. Hercules established dedicated facilities, such as the Hopewell plant in Virginia, to manufacture CMC under the trade name Cellulose Gum, facilitating its integration into adhesives, detergents, and coatings. Post-World War II expansion was propelled by global shortages of natural thickeners, positioning CMC as a reliable alternative amid disrupted supplies of plant-based gums from war-affected regions. The U.S. Food and Drug Administration (FDA) approved CMC as generally recognized as safe (GRAS) for food use in the 1950s, enabling its widespread adoption in processed foods for texture enhancement and stabilization. During the 1970s and 1980s, pharmaceutical applications surged, with CMC employed as a suspending agent, binder in tablets, and component in controlled-release formulations, supported by advancements in purification for biomedical purity. The evolution of production shifted from labor-intensive batch processes to more efficient continuous methods in the mid-20th century, improving yield and consistency through automated reaction and purification stages. Since the early 2000s, emphasis has grown on sustainable sourcing, utilizing agricultural wastes like sugarcane leaves and cotton scraps to reduce environmental impact and reliance on virgin wood pulp, aligning with global concerns over deforestation and resource depletion.

Chemical Structure and Properties

Molecular structure

Carboxymethyl cellulose (CMC) is derived from cellulose, a linear polysaccharide composed of β-1,4-linked D-glucose units forming the backbone. The modification involves the attachment of carboxymethyl groups (-CH₂COOH or, in its sodium salt form, -CH₂COONa) to some of the hydroxyl groups on the glucose rings via ether linkages, primarily at the C6 (primary alcohol), C2, or C3 positions. This substitution introduces anionic carboxylate groups, rendering the polymer water-soluble and polyelectrolytic when neutralized with sodium counterions. The degree of substitution (DS) represents the average number of carboxymethyl groups per anhydroglucose unit in the polymer chain, with a theoretical maximum of 3.0 (one per available hydroxyl group). Commercial grades typically exhibit DS values between 0.4 and 1.2, though ranges up to 1.5 are common in specialized applications; higher DS enhances solubility in water and influences solution viscosity by increasing chain hydrophilicity and electrostatic repulsion. The polymer chain of CMC is linear, consisting of repeating substituted glucose units. Sodium ions serve as counterions to the anionic carboxylate groups, stabilizing the structure in aqueous solutions. Molecular weight distribution, which varies across grades, is commonly analyzed using gel permeation chromatography (GPC) to assess chain length polydispersity. Structural variations in CMC include differences in chain length, leading to low-viscosity grades with shorter polymer chains (lower molecular weight) and high-viscosity grades with longer chains (higher molecular weight). These distinctions arise from controlled hydrolysis or polymerization during production. Confirmation of substitution patterns and DS is achieved through techniques such as Fourier-transform infrared (FTIR) spectroscopy, which identifies characteristic carboxylate peaks around 1600 cm⁻¹, and nuclear magnetic resonance (NMR) spectroscopy, which resolves proton and carbon shifts for positional analysis.

Physical and chemical properties

Carboxymethyl cellulose (CMC), typically in its sodium salt form, exhibits high solubility in water, with typical concentrations of 10–50 g/L (1–5%) and up to 100 g/L or more for low molecular weight grades, depending on the degree of substitution (DS) and molecular weight, while remaining insoluble in most organic solvents such as ethanol, acetone, and ether. This solubility arises from the hydrophilic carboxymethyl groups, enabling the formation of clear, viscous colloidal solutions or gels at concentrations exceeding 1% by weight. In mixed solvents like water-alcohol, CMC can precipitate, and solubility is influenced by factors including temperature and DS, with higher DS values enhancing water dispersibility. The rheological properties of CMC solutions are predominantly non-Newtonian, displaying pseudoplastic (shear-thinning) behavior where apparent viscosity decreases with increasing shear rate due to the alignment of polymer chains under flow. Viscosity spans a wide range of 10–100,000 cP, varying by grade, concentration, and measurement conditions, often assessed using a Brookfield viscometer at 25°C for a 1–2% solution. This shear-thinning is modeled by the power-law equation for non-Newtonian fluids: η=Kγ˙n1\eta = K \dot{\gamma}^{n-1} where η\eta is the apparent viscosity, γ˙\dot{\gamma} is the shear rate, KK is the consistency index, and n<1n < 1 is the flow behavior index indicating pseudoplasticity; alternatively, viscosity as a function of concentration CC follows η=KCm\eta = K C^m, with m>1m > 1 reflecting the strong concentration dependence. Chemically, CMC demonstrates good stability across a pH range of 2–10, where solutions remain viscous and undegraded, but it hydrolyzes under extreme conditions such as pH below 2 (precipitation) or above 12 (chain scission). It resists enzymatic attack from common cellulases due to substitution blocking active sites, though prolonged exposure to strong acids or bases can lead to depolymerization. Thermally, CMC is stable below 200°C but undergoes decomposition between 250–300°C, primarily via glycosidic bond cleavage and decarboxylation, with mass loss observed in thermogravimetric analysis. Additional properties include hygroscopicity, allowing CMC to absorb moisture from air and form stable hydrates, and a bulk density of approximately 0.3–0.8 g/cm³ for the powdered form. Ionic sensitivity is notable, as added salts like NaCl reduce solution viscosity by screening electrostatic repulsions between carboxymethyl groups, with effects more pronounced at lower concentrations and higher DS values. These attributes stem from the polyelectrolyte nature of CMC, briefly influenced by molecular structure details such as substituent distribution.

Production

Raw materials and process

Carboxymethyl cellulose (CMC) is synthesized primarily from high-purity cellulose, typically derived from wood pulp or cotton linters with a purity exceeding 95%. Key reagents include sodium hydroxide (NaOH) for activation, monochloroacetic acid (MCA) or sodium chloroacetate as the etherifying agent, and organic solvents such as isopropanol or ethanol to control viscosity and promote heterogeneous reaction conditions. The process commences with the activation step, in which cellulose is immersed in a concentrated NaOH solution (usually 18–40% w/v) at low temperatures (around 0–20°C) to form alkali cellulose. This treatment swells the cellulose structure, breaks hydrogen bonds between hydroxyl groups, and deprotonates the cellulose hydroxyls (Cell-OH → Cell-O⁻ Na⁺), enhancing their nucleophilicity for subsequent reaction. Etherification follows, where the activated alkali cellulose is mixed with MCA in the presence of the solvent and heated to 30–60°C for 1–3 hours. The reaction proceeds via a Williamson ether synthesis mechanism, with the cellulose alkoxide attacking the electrophilic carbon of the chloroacetate group to form the carboxymethyl ether linkage, introducing -CH₂COONa substituents onto the cellulose backbone. The primary reaction equation is: Cellulose-OH+ClCH2COONaNaOH, solventCellulose-O-CH2COONa+NaCl\text{Cellulose-OH} + \text{ClCH}_2\text{COONa} \xrightarrow{\text{NaOH, solvent}} \text{Cellulose-O-CH}_2\text{COONa} + \text{NaCl}
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