Aqueous dispersions of cellulosic material or cellulose derivatives and a process ofpreparing fibres, films and similar shaped articles of cellulose or of cellulose derivatives from such dispersions

摘要

A dispersion of cellulosic material nonpourable at 25 DEG C contains 9-30 per cent by weight of finely divided cellulosic material dispersed in an aqueous solution of calcium thiocyanate of 40-74 per cent by weight concentration. The cellulosic material has a degree of polymerization of at least 150, is insoluble in water and has at least 2.5 free hydroxyl groups per glucose unit. The particles of the cellulosic material should generally have at least two of their dimensions within the range 0.1 to 300 microns and, preferably, 0.1 to 100 microns. The greatest dimension of the particles should preferably not exceed 700 microns. The cellulosic material may be cellulose itself or a cellulose ether or ester. The weight ratio of calcium thiocyanate to cellulosic material is preferably at least 1.5 : 1, and the dispersion may be formed into a film, filament or other shaped article at 100-150 DEG C. under pressure. Preferably the shaped article is immersed in a coagulating bath and thereafter washed with water. The dispersions may be prepared with chemically purified wood pulp having fibres 1-2 microns in diameter and 35-165 microns long, or with cotton linters or long cotton fibres having fibre diameters of 0.1-100 microns ground to reduce their length to below 700 microns. Cellulose fibres and films regenerated from viscose and low-substituted methyl-, ethyl- or cyanoethyl-cellulose or cellulose acetate may be used. A form of activated cellulose particularly useful for the preparation of the dispersions is obtained by contacting cotton linters or wood pulp with a solution of sulphuric acid in glacial acetic acid (about 1.5 parts of sulphuric acid per 100 parts by weight of cellulose) and then reacting the cellulose with an alcoholic solution of a caustic alkali such as potassium hydroxide. Such regenerated and chemically treated celluloses may conveniently be mixed with the calcium thiocyanate solution in kneading-type mixers at 25 DEG to 120 DEG C. until uniform dispersions are formed. These dispersions may be converted into gels by heat or by working in a Banbury mixer at moderately elevated temperatures, and these gels may be converted into shaped articles. Alternatively the dispersions may be formed into shaped articles, without preliminary conversion into gels, by pressing, calendering or extruding at 100-150 DEG C. (preferably 100-135 DEG C.) at pressures of 10-1000 p.s.i. The resulting shaped articles may then be immersed in coagulating baths such as aqueous salt solutions, e.g. 25 per cent sodium or calcium chloride, 35 per cent magnesium chloride, 50 per cent sodium formate, 30 per cent sodium acetate, or 50 per cent aqueous glycerol or acetic acid, absolute alcohol, glycerol, methanol or acetone. The preferred coagulating bath is a 25 per cent aqueous sodium chloride solution. The shaped articles, e.g. fibres or films, are next washed in water until free from thiocyanate and the coagulating bath material, and dried at 25-50 DEG C. and 40-90 per cent relative humidity when unsoftened. In an example 10 parts of air dry finely divided chemically purified wood cellulose fibres of 3-50 microns in diameter and 50-170 microns average length (the cellulose having a D.P. of 380) are uniformly dispersed in a 56.7 per cent aqueous solution of calcium thiocyanate by shaking. After standing for 6 hours the dispersion becomes non-pourable at ordinary temperatures. It is warmed to 110 DEG C. and pressed hydraulically between sheets of aluminium foil at 100 DEG C. to form a film which separates spontaneously from the foil on immersion in water and is washed to produce a translucent gel cellulose film. This film is then immersed in 20 per cent aqueous glycerol for 30 minutes, squeegeed and dried on the squeegee plate to form a translucent, tough, pliable film. In a second example the above dispersion is extruded at 125 DEG C. and 53 p.s.i. to form a monofil which is washed in water and dried taut in air for 30 minutes. In other example films and filaments produced by extrusion form similar cellulose dispersions and from dispersions of methyl cellulose or low-substituted cyanoethyl cellulose are contacted with concentrated aqueous coagulating baths containing sodium acetate or sodium chloride. The limits of the operable proportions of cellulose, calcium thiocyanate and water for the preparation of the dispersions are shown by means of a graph having triangular co-ordinates. Concentrated aqueous solutions of lithium or ammonium thiocyanate, lithium bromide or calcium bromide, when used in place of calcium thiocyanate, form non-pourable dispersions, but films obtained from these are inferior in clarity and strength. When aqueous sodium chloride is used as the coagulating bath, the calcium thiocyanate may be recovered therefrom by evaporating off the water from the solutions until the concentration of the calcium thiocyanate reaches 50-60 per cent, when substantially all the sodium chloride crystallizes out and can be filtered off. The small amount of sodium chloride remaining in the solution does not interfere with the use of the solution in the preparation of the dispersions.