Patent GB-395353-A (GB)
Title: Improvements in or relating to solutions, compositions, preparations and articles having a basis of cellulose derivatives
IPC: C08J7/02
Filed: 1931-11-30
Abstract: Cyclic 1,3 diethers, other than methylene ethylene oxide, containing at least five atoms in the ring, are employed in the manufacture or treatment of filaments &c. of cellulose esters, ethers, and ether-esters, as solvents in the spinning solution or coagulating bath, or for swelling the threads for dyeing, printing, stencilling, discharging, delustring, relustring, improving, or stretching. Di-ethers, or their ethers or esters, obtained by condensation of an aldehyde or ketone with an aliphatic alcohol containing three or more hydroxy groups are excluded.  The di-ethers employed are good solvents for cellulose compounds of high ester or ether content, in some cases even for the tri-acetate itself.  Examples of the di-ethers are: 2 methyl-1 : 3-cyclo trimethylenedioxide (the ethylene glycol di-ether of acetaldehyde), 2 : 4-dimethyl-1 : 3-cyclotrimethylenedioxide, 2-methyl-1 : 3-cyclotetramethylenedioxide, 5 : 5-dimethyl-1 : 3-cyclotetramethylenedioxide, 4-chlormethyl-1 : 3-cyclo trimethylenedioxide, 2 : 2-diethyl-1 : 3-cyclo trimethylenedioxide, 4-methyl-1 : 3-cyclotrimethylenedioxide, 2-phenyl-1 : 3-cyclotetramethylenedioxide (obtained from benzaldehyde and 1 : 3-propylene glycol), 2-benzyl-1 : 3-cyclotrimethylenedioxide, the diether obtained from cyclohexanone with glycerol-monochlorhydrin, or the compounds obtained by condensation of formaldehyde or a polymer with diethylene or other polyolefine glycols.  Etherification catalysts may be employed in the condensation of the aldehydes or ketones with the aliphatic dihydroxy compounds.  For use as the sole or principal solvent in spinning solutions the lower di-ethers are suitable; for stretching or other treatment, the higher di-ethers. Other liquids which may be used in conjunction with the di-ethers are: acetone, methyl acetone, methyl acetate, ethyl acetate, ethers, esters, or ether-esters of olefine and polyolefine glycols, dioxane, methylene and ethylene chlorides, dichlorethylene, trichlorethylene, chloroform, alcohols, benzene, toluene, &c. ethers such as isopropyl ether, ethyl lactate, diacetone alcohol, and tetrachlorethane; for high volatility acetaldehyde, methyl formate, dimethylene dioxide; as high-boiling solvents or plasticizers, triacetin, diethyl phthalate, dibutyl phthalate, sulphonamides, such as alkylated xylene sulphonamides, sulphonanilides, tartrates, diphenylol propane, triphenyl phosphate, tricresyl phosphate (these two preferably with highly compatible plasticizers).  Other substances may be added, such as dyestuffs, pigments, or substances reducing flammability, such as tribrom-aceta-anilide.  From 5 to 8 per cent of water may sometimes be present.  The tendency of woven fabrics to slip, warp, split, or ladder may be reduced by treatment with a relatively volatile cyclic diether.  Filaments, artificial horsehair, &c., may be treated and allowed to shrink, to improve their extensibility or suppleness, or produce special effects. Tensile strength may be improved by stretching during or after treatment with the diethers, which if of high solvent power may be diluted with non-solvents such as water, benzene, or di-isopropyl ether.  The actual stretching force may be applied to a thread at a point where it has been freed again from solvent.  For facilitating textile operations, sizes may be applied which in addition to the di-ethers may contain thickening agents such as polymerized vinyl compounds or oxidized drying oils.  Absorption of liquid and solid materials by threads, fabrics, &c. may be facilitated by application of the di-ethers before or during dyeing, printing, discharging, loading, mordanting, or delustring. The materials thus applied may be acid wool and direct cotton dyestuffs, such vat dyestuffs as have little affinity, pigments, and formaldehyde sulphoxylate discharges.  Local or general relustring of materials which have been treated with wet steam may be effected by the di-ethers, with or without effect materials. In examples (1) cellulose acetate fabric, either lustrous or delustred, is printed with a mixture in specified proportions of a dyestuff or pigment, diethylene glycol, water, 1 : 3-tetramethylenedioxide, and gum arabic, dried steamed, washed, and soaped; (2) cellulose acetate yarn &c. in hank form is soaked for 2-5 minutes in a 30-40 per cent water solution of 4-chlormethyl 1 : 3-cyclotrimethylenedioxide and then gradually stretched by more than 100 per cent, say 500-700; or the stretching may be applied to filaments travelling in warp formation; (3) filaments &c. having an acetyl content of 57-58 per cent (as acetic acid) are soaked 2-5 minutes in a 45-50 per cent water solution of 2 : 4-dimethyl-1 : 3-cyclotrimethylenedioxide, and stretched as above; (4) a 25 per cent solution of cellulose acetate in 50 parts of acetone, 5 of water, and 45 of 2-methyl-1 : 3-cyclotrimethylenedioxide is spun into a cell at 75-90 DEG  C.; (5) a 22-25 per cent solution of cellulose acetate in 2 : 2-dimethyl-1 : 3-cyclotrimethylenedioxide containing 5-10 per cent of water is spun into a 50-60 per cent water solution of methyl glycol mono-acetate; the threads are drawn to fine denier by a rotating roller, washed with a more dilute solution or with a 30 per cent solution of sodium sulphate, washed with water, and dried; (6) a 22-25 per cent solution of cellulose acetate in acetone is spun into a water solution containing 12-15 per cent of diacetone alcohol and 15-25 per cent of 2 : 2-dimethyl-1 : 3-cyclotetramethylenedioxide, and treated as in example (5). According to the first Provisional Specification the di-ethers may be used in the manufacture of plastic compositions and films of cellulose compounds, and include di-ethylidene dioxide. Specifications 259,265, 277,089, 280,990, [all in Class 42 (i), Fabrics, Finishing &c.], 323,790, [Class 2 (ii), Cellulose &c.], 340,324, 340,325, 340,437, 370,430, 371,461, 380,504, 389,823, 391,769, 392,160, 392,186, 392,191, 394,015, and 394,016 are referred to.ALSO:Sizes for facilitating textile operations with thread made from cellulose esters, ethers, or ether-esters contain cyclic di-ethers having at least five atoms in the ring.  Examples of such di-ethers are: 2-methyl-1 : 3-cyclotrimethylene-dioxide (the glycol diether of acetaldehyde) 2 : 4 - dimethyl- 1 : 3- cyclotrimethylenedioxide, 2-methyl-1 : 3 - cyclotetramethylenedioxide, 5 : 5-dimethyl-1 : 3 - cyclotetramethylenedioxide, 4-chlormethyl-1 : 3-cyclotrimethylenedioxide, 2 : 2 diethyl-1:3-cyclotrimethylenedioxide, 4-methyl-1:3-cyclotrimethylenedioxide, 2-phenyl-1 : 3-cyclotetramethylenedioxide, 2-benzyl-1 : 3-cyclotrimethylenedioxide, the diether obtained from cyclohexanone and glycerol-monochlorhydrin, or the compounds obtained by condensation of formaldehyde or a polymer with diethylene or other polyolefine glycols.  As thickening agents may be used polymerized vinyl compounds or oxidized oils. Specifications 259,265, 277,089, 280,990, [all in Class 42 (i), Fabrics, Finishing &c.], 323,790, [Class 2 (ii), Cellulose &c.], 340,324, 340,325, 340,437, 370,430, 371,461, 380,504, 389,823, [all in Group IV], 391,769; 392,160, [Group IV], 392,186, 392,191; 394,015 and 394,016, [both in Group IV], are referred to.