DE690369C - Process for the production of nitrogenous cellulose derivatives - Google Patents

Description

Process for the production of nitrogen-containing cellulose derivatives Es it has been found that when epichlorohydrin acts on alkaline cellulose in the presence of ammonia or an ammonia derivative at ordinary temperature Under mild conditions, nitrogenous cellulose derivatives with changing., Form up to several percent to be increased nitrogen content. It is known, To etherify cellulose in acidic or neutral solution with epichlorohydrin and that To bring reaction product in a second stage with ammonia in reaction. Here elevated temperatures are used. It is also known to contain epichlorohydrin Let the alkali cellulose take effect. When treating the epichlorohydrin reaction product and alkali cellulose with ammonia, however, does not succeed, a nitrogen-containing one To produce cellulose derivative. It is also known to use haloalkylamines or haloaralkylamines to implement with alkali cellulose. This procedure has however with the simultaneous Effect of epichlorohydrin and an ammonia derivative on alkali cellulose nothing to do.

As cellulose starting material, cotton, linters, wood cellulose, Hydrate cellulose, e.g. B. in the form of rayon, staple fiber, film and the like mercerized cellulose from cotton: or wood pulp, in short all celluloses of any kind Origin and pretreatment serve: INTatron or potassium hydroxide solution is appropriate as alkali applied. -It is not necessary that the alkalis are essential for mercerization usual concentration of. z. B. r have 8% NaOH; rather, one already receives When using 2 to 4% sodium hydroxide solution, products with a significant nitrogen content. The cellulose material is impregnated with the alkali in the usual way by dipping and, if necessary, shredding the pressed alkali cellulose.

The action of the epichlorohydrin and the nitrogen derivative takes place at, ordinary temperature, expediently in vapor form, whereby by pumping the Vapor phase or by moving the alkalized. Cellulose for even exposure is to be taken care of. If the nitrogen component is a non-volatile or non-volatile substance is used, it is incorporated into the alkali with which the cellulose material is treated. Man. but can also the reagents in solvents such. B. in benzene, dissolved on the squeezed alkaline cellulose: let it take effect.

As nitrogenous components ammonia, primary, - secondary and tertiary amines with aliphatic, aromatic or mixed Radicals., OYalkylamines, amino acids, heterocyclic bases and their derivatives etc. are used.

The new cellulose derivatives keep their shape during implementation, z. B. the fiber shape. Show after washing off the excess alkali it is more or less depending on the nitrogen content and the basicity of the nitrogen component alkaline reaction. With acidic wool dyes, they dye quickly and quickly an., to be colored with weakly acidic. Dyes even deeper than in the same bath dyed wool.

Example i 50o g alkali cellulose from sulfite pulp with 29% cellulose and # i4) / 'o NaOH content are worked out in a thin layer, in an evacuated one Vessel exposed to the action of 13 g of liquid NH3 and after 2 hours 100 g Epichlorohydrin avoiding direct wetting of the alkali cellulose in the Given vessel. After standing for 18 hours at ordinary temperature, it is epichlorohydrin disappeared. The pure white product is diluted with water, sulfuric acid and washed out again with water and dried. Its nitrogen content is 1, 5 8 () / o.

Example 2 execution as in example i, only instead of i oo g Epi'chlorhydrin 200g applied. The reaction product contains 2.57% nitrogen.

Example 3 are 2oog linters. 3 hours in a dive site with _18% NaOH dipped, the one. Contains addition of glycocolla in the form of the sodium salt. The alkali cellulose is pressed to about 700g, shredded and vacuumed for 18 hours left to stand with 100 g of epichlorohydrin. The product contains after washing and drying 0.63 Ω / □ nitrogen.

EXAMPLE 4 160 g of mercerized and rewashed sulfite pulp are immersed in 150 g of 8% sodium hydroxide solution with a content of 1409 oxethylamine for 3 hours and pressed down to 540 g. The product is allowed to act in a vacuum of 100 g of epichlorohydrin in vapor form. After washing, the reaction product has 0.73% nitrogen.

EXAMPLE 5 160 g of the same mercerized cellulose as in Example 4 are immersed in 180% sodium hydroxide solution containing 50% anthranilic acid for 3 hours and pressed down to 950 g and fiberized. The alkali cellulose is exposed to the vapors of 100 g epichlorohydrin in a vacuum. The washed and dried product contains 0.2% nitrogen.

EXAMPLE 6 160 g of the same cellulose as in the previous example are immersed for 3 hours in 2oo /% sodium hydroxide solution, pressed onto 5009 and defibrated. The alkalized cellulose is exposed to the vapors of 13 g of ammonia and 100 g of epichlorohydrin in vacuo for 20 hours. The washed and dried product contains 0. g% nitrogen.

Example 7 Execution as in the previous example, only with 4% instead of 2% sodium hydroxide solution. The product contains 1,760f0 nitrogen.

Example 8 Execution as in example 6, only with 8% instead of 2% Caustic soda. The product contains 2,150/0 nitrogen.

Example 9 160 g of viscose staple fibers are dissolved in 2.8% strength potassium hydroxide solution 3 Hours. dipped, thrown off to 470.g, frayed and the vapors in a vacuum exposed to 13 g of ammonia and 10 g of epichlorohydrin for 18 hours. The conversion product shows after washing and drying 0.92 0'a nitrogen.

Example io Execution as in Example 9, but with 8.4% potassium hydroxide solution. The product contains 2.65% nitrogen.

Example ii 160g viscose staple fibers are immersed in 4% sodium hydroxide solution, squeezed to 5 i o g, shredded and in a vacuum under the action of 13 g ammonia and i oo g exposed to epichlorohydrin. The product contains i, 93% nitrogen.

EXAMPLE 12 A cotton skein weighing 20 g is used for 3 hours in. I 8% @ ger Caustic soda dipped and spun off to 63g. The skein becomes 18 hours long exposed to 2.1 g ammonia and i o g epichlorohydrin in a vacuum, Washed out with water, diluted acetic acid and again water .. That pure white The resulting cotton yarn contains 1.08% nitrogen.

EXAMPLE 13 A cotton yarn strand weighing 20 g is dissolved in i 8% sodium hydroxide solution, the 8.30 / 0 Oxät4ylamin. Contains, dipped and on 68 g thrown off. The strand is in a vacuum 2o hours the vapors of 13.5 g Epi- exposed to chlorohydrin. After leaving washing and drying are included in the construction want 0.78% nitrogen. Example 14 r6og viscose staple fibers are made with 4% Potash lye, soaked, to 41.0 g centrifuged <; frayed and in a vacuum the vapors vo! ri 13 g of ammonia exposed, with warming entry. After cooling down to Z: - @ i _ @,:, he temperature becomes a solution of jo: ., - #: Epi- chlorohydrin is absorbed in 2.51 benzene and the mixture was left to stand for 18 hours. After pressing and vacuuming the Benzene is used as in the earlier examples washed and dried. The product knows a nitrogen content of 1.19%. At the Instead of benzene, tetrachloride can also be used carbon can be applied. All percentages are by weight percentages.

Claims (1)

PATENT CLAIMS: 1. Process for the production of nitrogenous cellulose @ ederiva ° te, characterized in that alkaline cellulose of any origin and pre-treatment in the presence of ammonia or an ammonia derivative is exposed to the action of epichlorohydrin at normal temperature. a. Process according to Claim 1, characterized in that the epichlorohydrin and the nitrogen-containing reaction component both act on the alkali-containing cellulose in gas or vapor form. 3. The method according to claim 1, characterized in that .the nitrogen-containing component is brought onto the gelulose together with the dipping layer. 4. The method according to claim 1, characterized in that the E.pichlorhydrim is dissolved in .einem solvent for use.