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Sodium carboxymethyl cellulose (CMC Na) is an organic substance with the chemical formula [c6h7o2 (OH) 2och2coona] n. It is a carboxymethyl derivative of cellulose and the most important ionic cellulose gum. Sodium carboxymethyl cellulose powder is a kind of anionic high molecular compound usually prepared by reacting natural cellulose with caustic soda and monochloroacetic acid. Its molecular weight ranges from thousands to millions. CMC Na is a white fibrous or granular powder, odorless, tasteless, hygroscopic and easy to disperse in water to form a transparent colloidal solution.
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Morphological |
low visibility |
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Color |
white to light yellow |
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Melting point |
274 ° C (Dec.) |
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FEMA 2239 |
CARBOXYMETHYLCELLULOSE |
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Density |
1,6 g / cm3 |
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Storage conditions |
room temp |
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Acidity coefficient ( pKa ) |
4.30 (at 25 ℃) |
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PH value |
pH (10g / L, 25 ℃) 6.0 ~ 8.0 |
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Solubility H2O |
20 mg / ml, soluble |
Carboxymethyl cellulose sodium is widely used as a drilling mud treatment agent, synthetic detergent, organic cleaning aid, textile printing and dyeing sizing agent, water-soluble gel like thickening agent for daily chemical products, thickening agent and emulsifier for pharmaceutical industry, thickening agent for food industry, adhesive agent for ceramic industry, industrial paste, sizing agent for paper industry, etc. Used as a flocculant in water treatment, mainly for wastewater and sludge treatment, it can increase the solid content of the filter cake.
1. Thickening and emulsifying stabilization effects
Sodium carboxymethyl cellulose powder used for consumption can emulsify and stabilize beverages containing oil and protein. Generally, oil and protein beverages are characterized by varying degrees of fat and a certain amount of protein, which can easily separate and float during storage, forming an unsightly "collar" that affects the appearance of the product.
In addition, proteins are prone to coagulation and separation, especially in products with low pH values, and proteins are bound to coagulate. CMC Na can effectively solve these problems by dissolving in water as a transparent and stable colloid, which can stabilize proteins and reduce the surface tension between fat and water, allowing fat to be fully emulsified. Therefore, CMC Na is often used as a thickener in the food industry.
2. Water retention function
Sodium carboxymethyl cellulose has hydration effect. It can play the role of tissue improvement in meat products, bread, Mantou and other foods, and it can make water not volatile, improve product output and increase taste.
3. Gel
Sodium carboxymethyl cellulose with thixotropy refers to the interaction of a certain number of large molecular chains, which tends to form a three-dimensional structure. After forming a three-dimensional structure, the apparent viscosity of the solution increases; After breaking the three-dimensional structure, the apparent viscosity decreases. The phenomenon of thixotropy refers to the time-dependent change in apparent viscosity. The thixotropic carboxymethyl cellulose plays an important role in the gel system and can be used to make jelly and jam.
4. Film-forming property
Sodium carboxymethyl cellulose can form a film on the surface of food, which can provide certain protection for fruits and vegetables. Due to the presence of the film, a low oxygen, high carbon dioxide gas environment is formed between the film and the fruits and vegetables, thereby reducing the gas exchange rate and substance exchange rate, and extending the shelf life of fruits and vegetables.
Sodium carboxymethyl cellulose also has other properties such as suspension and chemical stability, which lay the foundation for its widespread application in the food industry.
5. Application in dairy products
(1) Application research in acidic beverages
Acidic dairy beverages have a unique sour and sweet flavor and have a wide market. However, during the production process, casein tends to aggregate and become unstable under acidic conditions. Therefore, polysaccharides are generally added to protect casein, stabilize the system, and ensure a good taste. The mechanism by which carboxymethyl cellulose sodium, as a polysaccharide, can stabilize acidic dairy beverages can be described as follows: during the acid adjustment process, when the pH value is 5.2, CMC Na begins to adsorb onto the surface of casein micelles, similar to the effect of kappa casein under neutral conditions.
The electrostatic repulsion and steric hindrance of the adsorption layer maintain the stable existence of casein micelles, and CMC Na has a thickening effect, which can reduce the settling rate of protein particles. The results indicate that at low pH values, a certain concentration of sodium carboxymethyl cellulose is required; And below this concentration, the system will lose stability. At pH values of 3.6~4.6, lower pH systems require more Sodium carboxymethyl cellulose powder for stability.
Fermented acidic dairy beverages have higher requirements for stabilizers compared to acid adjusted beverages.Acidic dairy beverages containing fruit granules require the addition of a certain amount of fruit granules to stabilize the system. The experiment showed that CMC Na is the main stabilizer for acidic dairy beverages. When CMC Na accounts for 0.4% and pectin accounts for 0.14% in the composite stabilizer, the system has better stability.Scholars have also studied the use of carboxymethyl cellulose sodium to stabilize the system in lycopene active beverages.
Research has shown that when the amount of CMC Na added is greater than 0.4%, the product has good stability, but the viscosity increases significantly at this time, so it can be used in combination with other colloids.
After optimizing the CMC Na cooling process, the viscosity of traditional acid regulating dairy beverages is always higher than that of heated products during the shelf life, providing better stability. This also provides a theoretical basis for the better application of carboxymethyl cellulose sodium in the production of acidic dairy beverages.
(2) Application in Blended Yogurt
The denaturation and precipitation of milk protein under acidic conditions has always been a key issue affecting the development of yogurt. Due to its multifunctional properties, abundant sources, and affordable price, CMC Na is commonly used as a stabilizer.
The results showed that CMC Na was greatly affected by temperature and pH value. When the amount of CMC Na added was small, the yogurt state could not be stabilized. When its content was greater than 0.4%, the yogurt state improved and the system tended to be stable; And the thickening effect of CMC Na on yogurt is relatively small at 0.05%~0.1%, while the thickening effect is significant in the range of high content (0.4%~0.5%).
(3) Application of casein lotion
Lotion is a dispersion system composed of one liquid dispersed in the form of tiny droplets in another immiscible liquid, which is an unstable system. Among numerous food gums, the product and xanthan gum have been extensively studied due to their unique functional properties. The results indicate that the combination of CMC Na and XG (xanthan gum) can make the system more stable. At a certain mixing ratio (CMC Na: XG is 1 ∶ 1, 3 ∶ 1), the total addition amount is 0.4% of the total mass of lotion, and the layering stability of lotion will increase. The layering phenomenon is not obvious when the emulsion is stored at room temperature for 2 weeks.
6.Application in the production of bread and Mantou
Sodium carboxymethyl cellulose has certain hydrophilicity and rehydration properties, therefore it is used in the production of flour products.
(1) Application in bread
Due to the presence of hydrophilic groups in carboxymethyl cellulose sodium, it can combine with water to form hydrophilic colloids and absorb water to expand. The expanded CMC Na can increase the water holding capacity of gluten, which is beneficial for the fermentation and baking process of bread and the retention of carbon dioxide, thereby increasing the volume of bread.
However, the amount of carboxymethyl cellulose sodium should not exceed 6%. Due to its strong water retention, the appropriate amount of addition can reduce the hardness of bread. The experiment showed that adding an appropriate amount (2%~8%) of carboxymethyl cellulose sodium significantly improved the quality of baked bread, with the best effect observed when adding 6%, followed by 4%. It can increase the volume of bread, improve the structure and flavor of bread, and extend the shelf life of bread. This provides the possibility for adding sodium carboxymethyl cellulose powder to bread to improve its quality.
(2) Application of in the production of Mantou
The addition amount of sodium carboxymethyl cellulose has little effect on the pH value of wheat Mantou dough. Research shows that sodium carboxymethyl cellulose can effectively improve the texture of wheat Mantou, and effectively reduce the hardness, adhesion, and chewiness of Mantou. When the addition amount of sodium carboxymethyl cellulose is 0.06%~0.08%, each texture index performs best. However, the application of sodium carboxymethyl cellulose in Mantou is still less, which also provides a possibility for its application in new fields and can increase its application range.
7. Other applications
Food thickeners have the characteristics of thickening, thickening, stability, salt and temperature resistance, and are widely used in food seasonings. Some scholars have studied the selection of thickening agent and process optimization in the preparation of natural meat essence. The results show that 5% carboxymethyl cellulose is selected as the colloid of meat essence, heated and dissolved in a water bath at 60~70 ℃, stirred for 30min, dissolved the colloid, placed for 24~48h, swelled and then used to prepare meat flavor monosodium glutamate. The product has good thickening property, colorless and tasteless.
Due to its thickening effect, sodium carboxymethyl cellulose can be used to make jam. After experimentation, it was found that the optimal process for making water chestnut tomato sauce is 1.9% sodium carboxymethyl cellulose, 0.8% citric acid, 4% white sugar, and a water chestnut sauce to tomato sauce ratio of 1:1. The resulting jam has a good taste and stability.
Sodium carboxymethyl cellulose can also be used to make beverages. Corn beverages are prone to layering and precipitation during storage, while the combination of CMC and sodium alginate can improve stability. When both carboxymethyl cellulose sodium and sodium alginate were added at a dosage of 0.05%, the precipitation rate of corn beverage was the smallest, and the stratification was not obvious after centrifugation, with good stability. This also laid a certain foundation for the development of the corn beverage market. Sodium carboxymethyl cellulose is also used in the production of ice cream and clarification of alcoholic beverages.
Preparation method of Sodium carboxymethyl cellulose powder:
The reaction system must be basic. This process belongs to Williamson ether synthesis method. The reaction mechanism is nucleophilic substitution. The reaction system is alkaline. In the presence of water, there are some side reactions, such as the formation of sodium hydroxyacetate, hydroxyacetic acid and other by-products.
Due to the existence of side reactions, the consumption of alkali and etherifying agent will be increased, thereby reducing the etherification efficiency; At the same time, sodium hydroxyacetate, hydroxyacetic acid and more salt impurities will be generated in the side reaction, which will reduce the purity and performance of the product.
To suppress side reactions, it is not only necessary to reasonably use alkali, control the amount of water system, the concentration of alkali and the stirring method, with the goal of fully alkalizing, but also to consider the requirements of the product for viscosity and substitution degree, and comprehensively consider the stirring speed, temperature control and other factors to improve the etherification rate and suppress the occurrence of side reactions.
According to the different etherification media, the industrial production of CMC Na can be divided into two categories: aqueous and solvent methods. The method using water as the reaction medium is called the water medium method, which is used to produce alkaline medium and low grade CMC Na. The method using organic solvent as the reaction medium is called the solvent method, which is suitable for the production of medium and high-grade CMC Na. These two reactions are carried out in a kneader, which belongs to the kneading process and is the main method for producing CMC Na at present.
Water medium method:
The water-based method is an earlier industrial production process, in which alkali cellulose is reacted with etherifying agent under the conditions of free alkali and water. There is no organic medium in the system during alkalization and etherification. The water medium method requires relatively simple equipment, less investment and low cost. The disadvantage is the lack of a large amount of liquid medium, the heat generated by the reaction increases the temperature, accelerates the speed of side reactions, leads to low etherification efficiency and poor product quality. This method is used to prepare middle and low grade CMC Na products, such as detergents and textile sizing agents.
Solvent method:
The solvent method is also known as the organic solvent method. Its main feature is that the alkalization and etherification reactions are carried out under the condition that the organic solvent is used as the reaction medium (diluent). According to the amount of reaction diluent, it can be divided into kneading method and slurry method. The reaction process of the solvent method is the same as that of the water-based method, which is also composed of two stages of alkalization and etherification, except that the reaction media of the two stages are different. The solvent method eliminates the inherent alkali leaching, pressing, crushing, aging and other processes of the water-based method, and the alkalization and etherification are carried out in the kneading machine. The disadvantages are relatively poor temperature controllability, space requirements and high cost. Of course, for the production of different equipment layouts, the system temperature and feeding time should be strictly controlled to prepare products with excellent quality and performance.
Sodium carboxymethyl cellulose powder is the most widely used and highest-volume cellulose derivative in the world. Its discovery and industrialization represent an important milestone in the fields of polymer materials and cellulose chemistry in the 20th century.
I. First Synthesis and Birth of the Patent (1918–1921)
In 1918, German chemist E. Jansen first prepared sodium carboxymethyl cellulose using natural cellulose (cotton linter, wood pulp) as raw material through alkalization followed by etherification with monochloroacetic acid. This technology overcame the limitation that natural cellulose is insoluble in water; the introduction of sodium carboxymethyl groups endowed it with excellent water solubility, thickening properties and stability.In 1921, Jansen was granted a patent for this synthesis, marking the official birth of CMC. Early products were crude and mainly used in Europe as colloids and binders, with a limited scope of application.
II. Industrial Advancement and Expanded Applications (1936–1945)
From 1936 to 1941, research on the industrial application of CMC was active, and numerous key patents promoted process optimization. During World War II, due to shortages in natural gum supply, Germany extensively used CMC as an anti-redeposition agent in synthetic detergents and as a substitute for natural colloids such as gelatin and gum arabic, significantly boosting its industrial scale.In 1943, Hercules Corporation of the United States realized the industrial production of CMC and solved challenges concerning purity and stability.
III. Refinement and Global Standardization (After 1946)
In 1946, Hercules launched high-purity CMC powder, which was recognized by the U.S. FDA as a safe food additive (E466). With its non-toxic, odorless, thickening, stabilizing and emulsifying properties, CMC quickly found applications in food, pharmaceuticals, daily chemicals, petroleum and other industries, earning the reputation of "industrial monosodium glutamate".It subsequently gained worldwide popularity, and China achieved industrial production of CMC in Shanghai in 1958.To this day, CMC remains the most important ionic cellulose ether, with continuously evolving manufacturing processes and expanding application scenarios.
FAQ
What is sodium carboxymethylcellulose powder used for?
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CMC could be used as flocculating agent, chelating agent, emulsifier, thickening agent, water-retaining agent, sizing agent, and film-forming material, and so on. CMC is also widely applied in fields such as electronics, pesticides, leather, plastics, printing, ceramics, and the daily-use chemical industry.
Is sodium carboxymethylcellulose healthy?
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Though it is recognized as safe by the EFSA and FDA, newer works have raised concerns related to its safety, as in vivo studies showed evidence of gut dysbiosis associated with CMC's presence.
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