DE1053719B - Process for the production of threads and films from copper oxide ammonia cellulose solution - Google Patents

Description

GERMAN

The purpose of the process is the production of artificial copper silk threads with previously unattainable standards high strength.

It is known to spin copper rayon by using the copper oxide ammonia cellulose spinning solution very slowly coagulated by warm water with bracing and thereby largely until it decomposes to hydrate cellulose. A subsequent extension is only possible to a limited extent up to a maximum of 5%. In order to modify the spinning conditions somewhat, the water is given a small amount of chemicals Quantities such as sodium hydroxide solution, calcium chloride or ammonia are added. You even have felling tracks of more than 1.5 m and spinning temperatures of 60 to 95 ° C must be accepted. All accessories but they do not change anything in the above-mentioned working principle of slow precipitation, they do not allow any higher post-drawing and thus also have the strengths of those spun according to this principle Rayon cannot increase.

It is also known that the copper ammonia cellulose solution by spinning in strong sodium hydroxide solution to transform into threads with 40 g of NaOH per liter and more. However, these cannot easily be re-stretched, but may have to wait outside of the spinning apparatus after some waiting time Hours before they can be stretched in warm solutions. You also have this one strongly alkaline precipitation baths copper carbonate is added to make the thread fuller and softer make, however, stretching and thus higher strengths were not achieved in this way.

With the so well-known process one has spun rayon, the strengths of in general 2 g / den have. In any case, it was not possible to exceed a value of 2.5 g / den.

It has now surprisingly been found that threads with dry strength values of 3 to 5 g / denier and wet strengths of 2 to 4 g / denier at dry and wet elongation of 5 to 12% and films with a strength of 15 kg / mm ^{2 are} obtained , if the copper oxide ammonia cellulose solution is sprayed into precipitation baths of a special composition, which cause very rapid coagulation without, however, leading to decomposition, and if the only coagulated structure is strongly stretched and only then decomposed. The felling baths that cause the aforementioned effect contain

(I) at least 2 mol / l alkali salts or a little

at least 0.1 mol / l soluble alkaline earth salts,
(II) up to 8 mol / l ammonia and
(III) Ammonia complexing agents in the form of their salts which are soluble in the bath in one up to the process

for making threads and films
from copper oxide ammonia cellulose solution

Applicant:

JP Bemberg Aktiengesellschaft,
Wuppertal-Oberbarmen

Dipl.-Chem. Dr. Horst Frind, Wuppertal-Langerfeld,
has been named as the inventor

Concentration reaching the saturation point.

Component (I) can optionally also consist of a mixture of alkali metal salts and alkaline earth metal salts exist. In this case the concentration is chosen so that the sum of the proportions, expressed in Percentage of the respective aforementioned minimum concentration, at least 100% achieved (see example 3).

The halides, nitrates and formates can be used as suitable alkali and alkaline earth salts and acetates. If only alkali salts are used, the sulfates and carbonates are also useful.

The optimum concentration of component (II) is reached when the bath contains ammonia the concentration of ammonia and spinning solution · contains the concentration corresponding to 3 to 4 mol / l.

Suitable ammonia complexing agents are the copper, zinc, cadmium, cobalt or nickel halides, nitrates, formates or acetates as well as the sulfates and carbonates of the metals mentioned in those cases in which no alkaline earth salts are contained in the bath. The concentration this bath component (III) reaches its optimum at 0.1 mol / l, which corresponds to the concentration of the unbound copper in the spinning solution.

Due to the presence of the alkali or alkaline earth salts in the precipitation bath, the coagulation of the Spinning solution caused. The components (TI) ammonia and (III) ammonia complexing agents have the task of suppressing the decomposition of the spinning or casting solution as much as possible. The ability to stretch the threads or films is on

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highest when the decomposition is practically zero. This is the case with the optimal concentrations mentioned of components (II) and (III) achieved. A further increase in the proportions of these compounds in the precipitation bath is permitted, but this does not improve the stretchability.

While the usual manufacturing processes of threads and films made from copper oxide cellulose solution in precipitation baths of at most 30 to 40% can be achieved according to the procedure according to the invention stretched by 50 to 200% before the decomposition of the thread or film is carried out. The structure of the structure is thereby compressed, and strength values are achieved that have not been achieved before could be achieved.

Following the stretching, it is decomposed in the usual way in acid baths.

As a technical advance, the process not only significantly increases the Strength achieved, but also a better and cheaper recovery of the expensive Chemicals copper and ammonia in that they are used in the spinning bath in much larger quantities Concentration than before.

Embodiments

1. A copper oxide ammonia cellulose solution with 9% cellulose, 6.5% ammonia and 3.8% copper MoVl T < ammonia and 0.1 mol / l copper chloride, injected into a monofilament thread and the thread, which is soon coagulated, is subjected to a stretching of 150%. After decomposition with hydrochloric acid and subsequent washing out of the copper chloride and the acid, a monofilament thread with a titer of 5 denier is obtained. Its textile data are: dry strength 5.2 g / den; Wet strength 4.4 g / den; Dry elongation 8% and wet elongation 5%.

2. A spinning solution of the above composition is pressed through a nozzle with a hole size of 0.1 mm into a precipitation bath which contains 5 mol / l sodium chloride, 0.05 mol / l CuCl ₂ and 3.7 mol / l ammonia. The coagulated monofilament thread is stretched, then-P decomposed with sulfuric acid and freed from copper sulphate and acid by washing out. At a denier of 8 denier, this thread has a dry strength of 3.0 g / denier, a wet strength of 2.1 g / denier, a dry elongation of 11% and a wet elongation of 7%.

3. A spinning solution of the above composition is passed through a nozzle with 24 holes into a spinning bath pressed, the 0.6 mol / l (= 600% of the minimum amount) calcium chloride, 1 mol / l (= 50% of the minimum amount) Contains sodium chloride (650% in total), 2 mol / l ammonia and 0.1 mol / l copper chloride. Of the coagulated thread is stretched 100% and then decomposed with hydrochloric acid and washed out decoppered and deacidified. The thread material has a titer of 60 den, a dry strength of 3.4 g / den, a wet strength of 2.3 g / den, a dry elongation of 10% and a wet elongation of 8%.

4. A spinning solution of the above composition is forced through a nozzle with 16 holes into a spinning bath, the 4 mol / l sodium chloride. Contains 0.2 mol / l ammonia and 0.01 mol / l copper sulfate. To a stretching of 50%, decomposition by sulfuric acid and leaching of the copper sulphate and the acid, the textile properties of the thread material are as follows: Titer: 40 den, dry strength: 3.2 g / denier, wet strength: 2.3 g / denier, dry elongation: 11% and wet elongation: 8%.

Claims (6)

Patent claims: 1. Process for the production of threads and films, from copper oxide ammonia cellulose solution with high strength values, characterized in that the spinning solution is placed in a bath sprays out which (I) at least 2 mol / l alkali salts or at least 0.1 mol / l soluble alkaline earth salts or a mixture of alkali and soluble alkaline earth salts in such a concentration contains that the sum of the proportions, expressed as a percentage of the respective aforementioned Minimum concentration, at least 100% achieved (II), up to 8 mol / l ammonia and (III) X ^ ammonia complexing agents in the form of their in that £ pad soluble salts in one to the saturation point contains sufficient concentration, whereupon the coagulated structure is strongly stretched, then decomposed by acid and then in a known manner by washing out from Copper salt and freed from the acid. 2. The method according to claim 1, characterized in that that the bath ammonia in a corresponding to the ammonia concentration of the spinning solution Contains concentration. 3. The method according to claim 1 and 2, characterized in that the alkali or alkaline earth metal salts the halides, nitrates, formates and acetates are used. 4. The method according to claim 1 and 2, characterized in that in the absence of earth 'ßiSL ^ alkali salts as alkali salts also alkali sulfates and : - ^^ carbonates are used.
Λ ^ Ι 5. The method according to claim 1 to 4, characterized ■ '' • marked that as ammonia complexing agents soluble in the bath Copper, zinc, cadmium, cobalt or nickel halides, nitrates and formates or acetates can be used in concentrations up to 0.1 mol / l. 6. The method according to claim 1 to 5, characterized in that also the sulfates and Carbonates of copper, zinc, cadmium, cobalt and nickel are used when there are no alkaline earth salts are present in the bathroom. Considered publications:
German patent specifications No. 154 507, 173 628,
158, 682 884, 286 297. © 809-787 / 530 3.59