Cellulose ethers, water

MEE Meerson, S.I., Shakhova, E.M., Prokofeva, M.V., and Khin, N.N., Distribution of electrolytes and phase equilibria in cellulose ethers-water-electrolyte systems (Russ.), Vysokomol. Soedin., Ser. A, 24, 634, 1982. 

Solutions of natural and synthetic high molecular mass substances in water, e.g., starch, dextrins, casein, cellulose ethers, water-soluble derivatives of poly(acrylic acid), poly(vinyl alcohol), poly(vinyl pyrrolidone) (adhesive sticks). Uses paper, fiberboard. Glutins (glues of animal origin). Uses wood, paper, fiberboard, moistenable adhesive tapes. 

Two important classes are cellulose esters (qv) and cellulose ethers (qv). Cellulose esters are not water soluble and are not discussed here cellulose ethers are an important segment of water-soluble polymers. 

Cellulosics. CeUulosic adhesives are obtained by modification of cellulose [9004-34-6] (qv) which comes from cotton linters and wood pulp. Cellulose can be nitrated to provide cellulose nitrate [9004-70-0] which is soluble in organic solvents. When cellulose nitrate is dissolved in amyl acetate [628-63-7] for example, a general purpose solvent-based adhesive which is both waterproof and flexible is formed. Cellulose esterification leads to materials such as cellulose acetate [9004-35-7], which has been used as a pressure-sensitive adhesive tape backing. Cellulose can also be ethoxylated, providing hydroxyethylceUulose which is useful as a thickening agent for poly(vinyl acetate) emulsion adhesives. Etherification leads to materials such as methylceUulose [9004-67-5] which are soluble in water and can be modified with glyceral [56-81-5] to produce adhesives used as wallpaper paste (see Cellulose esters Cellulose ethers). 

Water-Soluble Films. Water-soluble films can be produced from such polymers as poly(vinyl alcohol) (PVOH), methylceUulose, poly(ethylene oxide), or starch (qv) (see Cellulose ethers Polyethers Vinyl polymers). Water-soluble films are used for packaging and dispensing portions of detergents, bleaches, and dyes. A principal market is disposable laundry bags for hospital use. Disposal packaging for herbicides and insecticides is an emerging use. 

A number of after-treatments with polyester copolymers carried out after sodium hydroxide processing are reported to produce a more hydrophilic polyester fabric (197). Likewise, the addition of a modified cellulose ether has improved water absorbency (198). Other treatments used on cotton and blends are also effective on 100% polyester fabrics (166—169). In this case, polymeri2ation is used between an agent such as DMDHEU and a polyol to produce a hydrophilic network in the synthetic matrix (166—169). 

Cellulose Deriva.tives, Cellulose can be derivatized to make both water-soluble gums and hydrophobic polymers. The preparation of the hydrophobic cellulose esters (qv), cellulose acetates and cellulose nitrates, has already been mentioned. The water-soluble cellulose derivatives are cellulose ethers (qv). 

Unlike HEC and CMC, which are purified by washing with aqueous organic solvents, methylceUulose and its hydroxyalkyl modifications are purified in hot water where they are insoluble. As with other cellulose ethers, drying and grinding complete the process. 

Properties. Ethyl cellulose [9004-57-3] (EC) is a nonionic, organo-soluble, thermoplastic cellulose ether, having an ethyl DS in the range of 2.2-2.7. Actually, EC is water-soluble at DS 1.2, but only those products that are thermoplastic and soluble in organic solvents are of commercial importance, because of thek abiUty to form tough, stable films. Above a DS of about 2.5, EC is soluble in many nonpolar solvents. 

Properties. Hydroxypropylcellulose [9004-64-2] (HPC) is a thermoplastic, nonionic cellulose ether that is soluble in water and in many organic solvents. HPC combines organic solvent solubiUty, thermoplasticity, and surface activity with the aqueous thickening and stabilising properties characteristic of other water-soluble ceUulosic polymers described herein. Like the methylceUuloses, HPC exhibits a low critical solution temperature in water. 

Water RepeUency. The development of water-repellent cellulose ethers has been reviewed (55) (see Waterproofing). A typical example of a commercial etherification for waterproofing cotton is with stearamidomethylpyridinium chloride ... 

An example of the first type is the emulsion stabiliser as exemplified by sodium oleyl sulphate, cetyl pyridinium chloride and poly(ethylene oxide) derivatives. For a number of applications it is desirable that the latex be thickened before use, in which case thickening agents such as water-soluble cellulose ethers or certain alginates or methacrylates may be employed. Antifoams such as silicone oils are occasionally required. 

By use of a modification of the well-known Williamson synthesis it is possible to prepare a number of cellulose ethers. Of these materials ethyl cellulose has found a small limited applieation as a moulding material and somewhat greater use for surfaee eoatings. The now obsolete benzyl cellulose was used prior to World War II as a moulding material whilst methyl eellulose, hyroxyethyl eellulose and sodium earboxymethyl eellulose are useful water-soluble polymers. 

A number of water-soluble cellulose ethers are marketed." Methyl cellulose is prepared by a method similar to that used for ethyl cellulose. A degree of substitution of 1.6-1.8 is usual since the resultant ether is soluble in cold water but not in hot. It is used as a thickening agent and emulsifier in cosmetics, as a paper size, in pharmaceuticals, in ceramics and in leather tanning operations. 

Occasionally, water-soluble plastics are required. Poly(vinyl alcohol) is commonly the first to be considered but some cellulose ethers, polyethylene oxides, poly(vinyl pyrrolidone) and A-substituted polyamides are among many possible alternatives. 

Cellulose is also commercially modified by acetylation to produce a material suitable for X-ray and cine film. Commercially cellulose ethers are also prepared, such as methylcellulose. This material is water-soluble and gives a highly viscous solution at very low concentrations. Hence it is widely used as a thickener in latex paints and adhesives, in cosmetics and for coating pharmaceutical tablets. 

Fluidized aqueous suspensions of 15% by weight or more of hydroxyethyl-cellulose, hydrophobically modified cellulose ether, hydrophobically modified hydroxyethylcellulose, methylcellulose, hydroxypropylmethylcellulose, and polyethylene oxide are prepared by adding the polymer to a concentrated sodium formate solution containing xanthan gum as a stabilizer [278]. The xanthan gum is dissolved in water before sodium formate is added. Then the polymer is added to the solution to form a fluid suspension of the polymers. The polymer suspension can serve as an aqueous concentrate for further use. 

Semisynthetic gels are also very useful for the creation of drug delivery systems. Cellulose ethers are particularly important in drug delivery. These compounds are made by derivatizing the cellulose hydroxyls with various groups such as hydroxypropyl, methyl, or carboxymethyl. This substitution breaks up the crystallinity of native cellulose and makes it water-soluble [23], The degree... 

IX. Cellulose Ethers Soluble in Dilute Alkali but not in Water. 293... 

Cellulose ethers of a high degree of substitution are stable, relatively nonflammable, resistant to ultra-violet light and compatible with a wide range of solvents and plasticizers. Certain ethers of a low degree of substitution are soluble in water or alkali. It would appear from these properties that cellulose ethers should be ideally adapted for use in the plastics field and for many other uses. 

ADSORPTION AND INTERLAYER EXPANSION OF CELLULOSE ETHERS FROM FRESH WATER ON PEPTIZED SODIUM MONTMORILLONITE... 

A new class of water-soluble materials [10,11], was developed as a result of such design parameters that will be referred to as double substituted cationic cellulose ethers (DCEs). These materials contain both a cationic substituent and a hydrophobic substituent, attached to a cellulose ether backbone. The use of a double-substituted hydrophobe modified cationic polysaccharide is fundamentally different from current commercial vaginal formulations, which rely exclusively on nonionic or anionic vehicles. 

A proven solution to the binder problem is to use water insoluble organic polymer binders instead of clay. For example cellulose acetates and cellulose ethers binders are successfully employed to make commercial zeolitic adsorbents for sugar separation in aqueous solutions [154, 205, 218-223, 225-226, 231-232, 238]. This technique allows the use of zeoHte adsorbents in aqueous separation processes. 

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