Esterification, cellulose, with acid

The various ways in which esters of cellulose and phosphorous adds can be synthesized are esterification cellulose with free acids alcoholysis, with cellulose, of the esters and amides of phosphoric adds and esterification with mixed anhydrides df phosphoric adds and carboxylic adds. 

The acylation of cellulose with acid chlorides in DMA/LiCl is most suitable for the homogeneous synthesis of readily soluble partially functionalized long-chain aliphatic esters and substituted acetic acid esters (Table 16.3). In contrast to the anhydrides, the fatty acid chlorides are soluble in the reaction mixture and soluble polysaccharide esters may be formed with a very high efficiency. Even in the case of stearoyl chloride, 79 per cent of the reagent is consumed for the esterification of cellulose. 

Partially acetylated cellulose (i.e., cellulose with less than three ester groups per repeat unit) is produced by an indirect route. Direct synthesis yields an inhomogeneous product due to insolubility of cellulose in the reaction mixture. Some chains are completely acetylated while others may be completely unreacted. A partially acetylated product is usually produced by controlled hydrolysis of the triacetate. The triacetate is soluble in the reaction mixture and complete solubility ensures that the final product will be more homogeneous. Hydrolysis of the triacetate is carried out by controlled reversal of the esterification reaction by the addition of water or dilute acetic acid. 

Two methods of prepn are listed in Ref 3 a)By esterification of lactic acid with ethanol and b)By combining acetaldehyde with hydrocyanic. acid to form acetaldehyde cyanohydrin, and this is treated wi th ethanol HC1 to ethyl lactate. Used as a solvent for cellulose acetate and nitrate, other cellulose esters, resins, lacquers, paints and enamels Refs l)Beil 3, 264, 267, 280,(102,109) ... 

Nitrocellulose is obtained by esterification of cellulose with nitric acid. This process is described simply as nitration or more exactly O-nitration. The nitration of cellulose can be expressed by means of the following equation ... 

Cellulose esters (e.g., cellulose triacetate, cellulose diacetate, cellulose propionate, and cellulose butyrate) are prepared by initially treating cellulose with glacial acetic acid (or propionic acid and butyric acid) followed by the corresponding acid anhydride with a trace of strong acid as a catalyst in chlorinated hydrocarbon. Complete esterification reactions result in the formation of a triester, which undergoes water hydrolysis to form a diester. Cellulose acetate alone or in combination with cellulose triacetate or cellulose butyrate is used as a semipermeable membrane for osmotic pumping tablets, primarily in controlled release systems. The permeability of the membrane can be further modulated by adding water-soluble excipients to the cellulose esters. 

O-nitration of cellulose with mixtures of acids is a widely applied type of esterification reaction in a heterogeneous system. One of the factors influencing the reaction rate here is the rate of diffusion of the acid into the fibre. 

The influence of sulphuric acid in O-nitration processes, as for example in the esterification of cellulose with a mixture of sulphuric and nitric acids, appears to be somewhat different. This will be dealt with in the chapter on esters (Vol. II). 

Cellulose can be esterified by reacting with acids, acid chloride, anhydrides, or unsaturated agents [5,73] such as CS2, phenyl isocyanate [128,145] and urea. Model Glucosides. The esterification of simple glycoside in homogeneous system generally indicated [84,141] that the 6-OH group is more reactive... 

A relatively novel class of derivatives is obtained by the covalent incorporation of organometallic moieties into cellulose. For example, cellulose ferro-cenyl derivatives have been prepared by esterification of cellulose with an intermediate derived from ferrocene carboxylic acid and triphenyl phosphite in the presence of pyridine [84]. An enzymatically cleavable cellulose ester has been developed [85], and prodrugs have been coupled to the hydroxyl or carboxyl functions of C-terminal aromatic amino acids of cellulose peptide derivatives for controlled release applications [86]. 

A conaparison of the results of potentiometric titration of preparations of the starting cellulose and of the phosphorylated cellulose has shown that the latter contains acidic hydroxyl grou] It has also been found that all of the reaction products obtained contain methoxyl groups. These rraults, together with data frcan chromatographic studies, show that the phosphorylation erf cellulose with monomethylphosphite involves the simultaneous occurrence of the esterification and transesterification reactions. 

It is natural that with the growing interest in cellulose acetate, chemists have investigated other organic cellulose esters. Cellulose formate, the ester of the lowest member of the fatty acid series, has been studied. sufficiently to show that it is unlikely to be of commercial im-portance. It is difficult to produce a high degree of esterification of cellulose with this acid, and the ester which is obtained is very limited in solubility, and is highly unstable toward moisture and elevated temperatures. 

Various details of procedure are known for the esterification of cellulose with acetic anhydride in acetic acid. solvent. The factors of pretreatment, catalyst concentration, acetylation temperature and time of reaction are kept in balance in order that products of satisfactory appearance and the desired range of viscosity will be obtained. Modifications of this general formula usually involve the use of different solvents to replace part or all of the acetic acid. 

All esterification processes with acetic anhydride yield the fully esterified ester as the first soluble product. If the reaction medium is a solvent for the triester a solution is obtained, and if a reaction which retains the fiber structure is employed, samples taken at intervals are all insoluble in solvents until complete esterification is attained. The process in this way differs from nitration, in which soluble, partially esterified products are obtained by adjustment of the concentration of the nitration acids. In the etherification of cellulose, the ethers (e.g., methylated cellulose) prepared by partial substitution are also soluble products, exhibiting continuous, gradual changes in solubility characteristics with increasing substitution. 

The abnormal viscosities appear to be caused by combination of the metal ions with acid groups. These may be sulfate groups from the catalyst employed in esterification, or carboxyl groups present in the cellulose or introduced during purification. 

To evaluate the cellulose reactivity with respect to the esterification reactions, the amount of chemically bound phosphorus in impregnated materials was determined and related to the amount of acid and pretreatment temperature. Two celluloses with a... 

Nitric Acid and Nitrate Activation. The reactions of HNO3, nitrates, and nitrogen oxides with lignocellulosic materials have been a subject of numerous publications. The specific transformations can be subdivided into acid reactions, oxidation reactions, and nitration-esterification reactions. With HNO3 and more acidic salts the acid reactions predominate at higher dilutions, and parallel those of aqueous solutions of H2SO4 and other similar acids. Oxidation of cellulose results primarily in oxidation of primary hydroxyls to carboxyls, with the secondary hydroxyls oxidized less. Nitration leads... 

Pretreatment/activation involves swelling mostly chemical pulp fibers with glacial acetic acid and 4-7% moisture (on cellulose basis). Activation ensures uniform acetylation. Esterification involves the treatment of preactivated cellulose with a mixture of acetic acid and acetic anhydride at a consistency of about 10%. The acetic anhydride content of the mixture is approximately 25%, and this amounts to a 10-40% excess over stoichiometric requirement. The reaction proceeds at 50 °C. Hydrolysis refers to a process step in which the DS of the esterification product is reduced from its level of >2.9 to a level between 2.3 to 2.7 by the addition of 5 to 10% water. The temperature during hydrolysis is maintained at 40 to 80 °C. The consequence of hydrolysis is a uniform release of acetyl groups from the cellulose backbone so as to assure uniform solubility. Precipitation involves either the addition of the acetylation mixture into water or dilute acetic acid to produce a flake product, or the addition of water... 

Among the esters with organic acids, cellulose acetate is the most important one. Cellulose acetate has numerous uses such as manufacture of yarn, photographic films, lacquers, etc. Cellulose can be acetylated starting with lower levels of esterification up to the formation of cellulose triacetate. The acetate is obtained from the reaction of cellulose with acetic anhydride, usually in the presence of a catalyst such as H2SO4 or HCIO4. Numerous industrial procedures are known for this process [43]. 

Several commercial flame-resistant finishes are based on esterification of the cellulose with phosphoric acid (Perfect, y.S.D.C., 1958, 74, 829) ... 

Esterification of cellulose with phosphoric acid yields a product which is not inflammable, but is of no use because the loss of tensile strength is excessive. The loss of strength is avoided if the esterification is carried out in the presence of urea (Brit. Pat. 604197) or cyanamide (Brit. Pat. 634690). The treated fabrics, however, are rather brittle and the flame-resisting effect does not stand up to repeated washings. 

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