Patent GB-488707-A (GB)
Title: Process for the production of cellulose esters
IPC: C08B3/00
Filed: 1936-10-12
Abstract: For producing stabilized cellulose esters having an acyl content markedly lower than that of the triester, cellulose is esterified by the non-solvent method in the presence of a compound capable of supplying sulphuric acid radicles, and the content of sulphuric acid radicles, which determines the acyl content of the final ester, is controlled by adjustment of (a) the proportion between the quantity of esterifying agent and the quantity of compound capable of supplying sulphuric acid radicles, (b) the proportion between the quantity of compound capable of supplying sulphuric acid radicles and the quantity of cellulose and (c) the solvent power of the diluent preventing dissolution of the cellulose ester for the compound capable of supplying sulphuric acid radicles, and the removal of the sulphuric acid radicles from the intermediate mixed ester is effected with agents selected from those set forth in Specifications 411,260 and 468,880 which do not contain unesterified carboxylic radicles and/or hydroxyl groups, i.e. agents represented by the general formula R1(OR11)n(COOR111)m in which R1, R11 and R111 stand for a hydrocarbon residue (which may contain halogen, nitro or other substituents), R1 may also be absent or indicate hydrogen, and n is equal to zero or more and m is equal to one or more.  Examples of such agents for removal of the sulphuric acid radicle are ethyl acetate, isopropyl acetate, butyl acetate, ethylene glycol diacetate, cyclohexyl acetate, acetate of ethylene glycol monomethyl ether and of ethylene glycol monoethyl ether, ethyl propionate, ethyl oxalate and amyl formate. Substances capable of supplying sulphuric acid radicles are sulphuric acid and esters thereof, chlorsulphonic acid, sulphur trioxide and sulphuryl chloride.  As catalysts, sulphuric acid, phosphoric acid, hydrochloric acid, perchloric acid, salts of perchloric acid, methane monosulphuric acid and methane disulphuric acid may be used.  For the production of a cellulose acetate having an acetic acid content lower than 61 per cent, a ratio of acetic anhydride to sulphuric acid of 30 to 1 or less may be used together with a diluent comprising a liquid hydrocarbon. When large quantities of sulphuric acid are used, too strong a degradation of the cellulose is avoided by refrigeration, or a part or the whole of the sulphuric acid is fixed in the cellulose by means of a pretreatment with a mixture of fatty acid and sulphuric acid.  Before removal of the sulphuric acid radicles from the intermediate mixed ester, the residues of the esterification bath are moved by extraction, displacement, washing, centrifuging or filtering using e.g. an alkyl ester.  It is preferable also to remove residual sulphuric acid absorbed in the cellulose by washing at low temperatures with liquids having strong-dissolving power for sulphuric acid.  The removal of the sulphuric acid radicles may be effected continuously by treating the agent, e.g., alkyl ester or the like, with insoluble neutralizing agents, e.g., barium or calcium carbonate or a basic silicate, or with small quantities of alcohol.  Non-solvent diluents may be added to the agent used to eliminate the sulphuric acid radicles in order to avoid dissolution of the cellulose ester.  The products containing high proportions of acyl radicles, e.g., 58-61 per cent in the case of the acetate, are particularly useful for the manufacture of threads, films, plastics, and varnishes.