Xanthate rayon

Cellulose is the most abundant naturally oeeurring polysaccharide formed out of glucose-based repeat imits, connected by 1,4-beta-glucosidic linkages. Cellulose and its derivatives are widely used as tough versatile materials. Cellulose nitrate, cellulose acetate (CA) and cellulose xanthate (rayon) can be easily molded or drawn into fibers for textile applications, for designing composite materials (safety glass), as thermoplastics etc [80]. 

Rayon. Viscose rayon is obtained by reacting the hydroxy groups of cellulose with carbon disulfide in the presence of alkali to give xanthates. When this solution is poured (spun) into an acid medium, the reaction is reversed and the cellulose is regenerated (coagulated). 

The cellulose molecule contains three hydroxyl groups which can react and leave the chain backbone intact. These alcohol groups can be esterified with acetic anhydride to form cellulose acetate. This polymer is spun into the fiber acetate rayon. Similarly, the alcohol groups in cellulose react with CS2 in the presence of strong base to produce cellulose xanthates. When extruded into fibers, this material is called viscose rayon, and when extruded into sheets, cellophane. In both the acetate and xanthate formation, some chain degradation also occurs, so the resulting polymer chains are shorter than those in the starting cellulose. 

Originally, the word rayon was appHed to any ceUulose-based man-made fiber, and therefore included the cellulose acetate fibers. However, the definition of rayon was clarified in 1951 and includes textiles fibers and filaments composed of regenerated cellulose and excludes acetate. In Europe the fibers are now generally known as viscose the term viscose rayon is used whenever confusion between the fiber and the cellulose xanthate solution (also called viscose) is possible. 

In theory, for regular rayon manufacture only one of the hydroxyl groups on each pair of anhydroglucose units needs to be replaced by a xanthate group, ie, the target degree of substitution (DS) is 0.5, which if achievable without waste would need 23% CS2 on ceUulose. 

The formaldehyde approach is stiU used by Futamura Chemical (Japan). They make spun-laid viscose nonwovens where the hydroxymethylceUulose xanthate derivative formed from formaldehyde ia the spia bath allows the fibers to bond after layiag. This process was originally developed by Mitsubishi Rayon (30), who later found that the derivative was thermoplastic, and the web could be calender-bonded (120°C) prior to regeneration (31). 

Neste patented an industrial route to a cellulose carbamate pulp (90) which was stable enough to be shipped into rayon plants for dissolution as if it were xanthate. The carbamate solution could be spun into sulfuric acid or sodium carbonate solutions, to give fibers which when completely regenerated had similar properties to viscose rayon. When incompletely regenerated they were sufficientiy self-bonding for use in papermaking. The process was said to be cheaper than the viscose route and to have a lower environmental impact (91). It has not been commercialized, so no confirmation of its potential is yet available. 

Several cellulose esters (qv) are prepared commercially. Cellulose xanthate [9032-37-5] is made by reaction of cellulose swollen in 8.5—12% sodium hydroxide solution (alkaU cellulose [9081-58-7J) with carbon disulfide and is soluble in the alkaline solution in which it is made. When such a solution, termed viscose, is introduced into an acid bath, the cellulose xanthate decomposes to regenerate cellulose as rayon fibers or cellophane sheets (see Fibers, REGENERATED CELLULOSICS). 

Reaction of alkali cellulose with carbon disulphide to produce a cellulose xanthate which forms a lyophilic sol with caustic soda. This may be extruded into a coagulating bath containing sulphate ions which hydrolyses the xanthate back to cellulose. This process is known as the viscose process and is that used in the manufacture of rayon. 

When ethanol is replaced by cellulose, sodium cellulose xanthate is obtained this dissolves in aqueous alkali to give a viscous solution (viscose) from which either viscose rayon or cellophane can be obtained by adding acid to regenerate the (reconstituted) cellulose. Trithiocarbonates (CS3 "), dithiocarbonates (COS2 "), xanthates (CS2OR ), difhiocarbamates (CS2NR2 ) and 1,2-dithiolates have an extensive coordination chemistry which has been reviewed. ... 

This term was originally intended to denote all kinds of man-made textile fibres, but is now applied only to cellulose types. Viscose rayon (regenerated from a solution of cellulose xanthate in sodium hydroxide) accounts for the greater part of world rayon production. Acetate rayon and cuprammonium rayon are relatively unimportant. 

That type of rayon which is regenerated from viscose, a syrupy liquid consisting mainly of a solution of cellulose xanthate in dilute sodium hydroxide. 

Salts of the series of xanthic acids of the general formula ROCSSH. Certain xanthates such as ZIX are ultra accelerators for mbber. Cellulose xanthate is the intermediate product in the manufacture of viscose. See Viscose Rayon. Xanthogen Sulphide... 

Viscose Also known as the Cross-Bevan-Beadle process. A process for making regenerated cellulose fibers. The product has been known by the generic name rayon since 1924. Cellulose, from cotton or wood, is first reacted with sodium hydroxide ( mercerization), yielding alkali cellulose. This is dissolved in carbon disulfide, yielding cellulose xanthate, which is dissolved in sodium hydroxide solution. Injection of this solution (known as viscose... 

In 1891, British chemistry Cross and Bevan discovered that wood pulp when treated with sodium hydroxide solution and carbon disulphide, gets converted into cellulose xanthate. When cellulose xanthate is dissolved in caustic soda solution it gives a viscous solution that could be spun to form fibres called Viscose Rayon. Rayon is produced in large scale today in many countries including India. Rayon (also know as viscose) is in fact regenerated cellulose. 

One of the earlier methods was to treat cellulose with sodium hydroxide and carbon disulfide to obtain xanthate esters which could be dispersed in water and cast into sheets or spun into fibers. Subsequent treatment with acid decomposed the xanthates and gave regenerated cellulose, either in fiber or film form. The fibers were called viscose rayon and the films were named cellophane. Cellophane is still used as a wrapping film and some of it is still manufactured by the xanthate process. By treatment with nitric acid, cellulose was converted to a trinitric acid ester, which could be cast into units which were satisfactory for making gun cotton for a smokeless powder for either artillery shells or shotgun ammunition. It was quite insoluble but it could be converted to a jelly-like mass, which could be shaped into a desired form for ammunition use. Under milder conditions, a lower nitrate... 

Treatment of cellulose with a mixture of sodium hydroxide (NaOH) and carbon disulfide (CS2) yields cellulose xanthate. The action of acid on cellulose xanthate produces rayon or cellophane. 

The important fiber rayon is simply regenerated cellulose from wood pulp that is in a form more easily spun into fibers. Cellophane film is regenerated cellulose made into film. One method of regeneration is formation of xanthate groups from selected hydroxy groups of cellulose, followed by hydrolysis back to hydroxy groups. 

Cellulose is sometimes used in its original or native form as fibers for textile and paper, but is often modified through dissolving and reprecipitation or through chemical reaction. The xanthate viscose process, which is used for the production of rayon and cellophane, is the most widely used regeneration process. The cellulose obtained by the removal of lignin from wood pulp is converted to alkali cellulose. The addition of carbon disulfide to the latter produces cellulose xanthate. 

Regenerated proteins from casein (lanital), peanuts (ardil), soybeans (aralac), and zine (vicara) are used as specialty fibers. Regenerated and modified cellulose products, including acetate, are still widely used today and the production of fibers is similar to that described above for synthetic fiber production. Most regenerated cellulose (rayon) is produced by the viscose process where an aqueous solution of the sodium salt of cellulose xanthate is precipitated in an acid bath. The relatively weak fibers produced by this wet spinning process are stretched to produce strong rayon. 

Geometric effects coupled with diffusion and nucleation usually control the rates of all solids deposition phenomena. Such effects can be put to good use in the production of special products such as cellulose yarn (rayon), by the precipitation of cellulose in filament form as it emerges as sodium cellulose xanthate liquid from the spinnerets into a bath containing sulphuric acid, which extracts the sodium as sodium sulphate, and the carbon disulphide. In a similar manner, the fabrication of aromatic polyimide fibres is performed by dissolving the polymer in concentrated sulphuric acid and forcing the solution through spinnerets into water. 

Amongst the important chemical conversions of macromolecular substances are the various reactions of cellulose. The three hydroxy groups per CRU can be partially or completely esterified or etherified. The number of hydroxy groups acetylated per CRU are indicated by the names, i.e., cellulose triacetate, cellulose 2-acetate, etc. Another commercially important reaction of cellulose is its conversion to dithiocarboxylic acid derivatives (xanthates). Aqueous solutions of the sodium salt are known as viscose they are spun into baths containing mineral acid, thereby regenerating the cellulose in the form of an insoluble fiber known as viscose rayon. 

The natural fibers obtained from cotton, wood, flax, hemp, and jute all are cellulose fibers and serve as raw materials for the textile and paper industries. In addition to its use as a natural fiber and in those industries that depend on wood as a construction material, cellulose is used to make cellulose acetate (for making rayon acetate yarn, photographic film, and cellulose acetate butyrate plastics), nitric acid esters (gun cotton and celluloid7), and cellulose xanthate (for making viscose rayon fibers). The process by which viscose rayon is manufactured involves converting wood pulp or cotton Iinters into cellulose xanthate by reaction with carbon disulfide and sodium hydroxide ... 

Interest in the xanthates of carbohydrates has arisen almost entirely through the importance of the viscose process in the technical production of rayon and related products.126 The selective character of the reaction of carbon disulfide and alkali with polyhydroxy compounds has been studied. Lieser and Nagel126 found that a monoxanthate is formed with polyhydric alcohols and methyl a-D-glucopyranoside when they react with carbon disulfide and aqueous barium hydroxide. The xanthation that has been demonstrated in the cases of glycerol 1,3-dimethyl ether and levoglucosan (LXIX) shows that secondary hydroxyl groups can... 

Chemical reaction methods are effective in destroying the crystallinity of cellulose. For example, xanthation can decrystallize cellulose (34), but such elaborate processes appear much too costly unless cellophane or rayon fibers are the objectives. One route that might be effective and economical would be treatment of crystalline cellulose with alcohol in the presence of acid catalysts. Low-molecular-weight acetals may be formed, which could plasticize the cellulose at the same time that the degree of polymerization is reduced. 

Regenerated cellulose fibers are known as rayon and regenerated films as cellophane. They are made by the xanthate process, which uses sodium hydroxide and carbon disulfide ... 

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