DE954547C - Process for the production of artificial structures, such as threads or films, from viscose - Google Patents

Description

(WiGBl. P. 175)

ISSUED DECEMBER 20, 1956

A 1103p IVcI 2pb

The invention relates to a method

for the production of artificial structures, such as threads, tapes or films, made of viscose, in which a cation-active compound for the application

comes.

Such a method has become known from Dutch patent specification 39 956, in which it is described becomes, like the growth of the spinneret holes when spinning viscose rayon, xo especially when using a zinc-containing spinning bath, by adding cationic compounds, either to the spinning bath or to viscose, can be prevented.

The cation-active compounds can already be used in a very early phase of the preparation of the viscose be admitted, and it is even possible to do this Adding compounds to the cellulose (see British patent 590 064).

It is also known that when viscose is spun a so-called "milkiness" in the finished product Product is created. This "milkiness", which has an unfavorable effect on the appearance of the product, can be stopped in a known manner by changing the spinning circumstances, z. B. by Spinning at a lower chlorammonium number or a higher hemicellulose content in the Viscose. Because these means, however, often have an unfavorable influence on other properties, such as Strength, elasticity and coloration, if one looked for means, have this "milkiness"

to prevent without adversely affecting the other properties. By adding certain anion-active compounds to viscose can completely avoid the occurrence of "milkiness" will. The best results are obtained with highly sulfonated, non-mineral oils (see the Dutch patent 28550). Other anion-active or inionogenic substances can also be used for this Purpose come to use (see British patents 526206 and 526207).

It has already been proposed to use combinations of anionic and cationic compounds of the Adding viscose, which turned out to be possible, in spite of the antagonistic nature of this two types of connection to obtain a beneficial effect (see Dutch patent specification 60 507).

According to the invention it has now been found that it

there are a certain kind of cation-active substances, which in addition to the already known property of Preventing the nozzle holes from growing, surprisingly produce a completely new effect, namely, that these cation-active substances at the same time "milkiness" encounter in the products spun from the viscose.

The method according to the invention is characterized in that a cation-active substance of formula

is used in which R _{1 is} an aliphatic chain with at least 8 carbon atoms in the molecule and R ₂ and R _{3 are} alkylene oxide chains, which are represented by - '(C _n H _2n O) _x H, in which χ for R , and R ₃ can be different, but in such a way that in any case the total number of groups of R ₂ and R _{3 is} at least 5 and χ can not be zero in either of the two groups.

It is advantageous if the aliphatic chain of R _{1 contains} 8 to 24 carbon atoms in the molecule, and compounds in which this number of carbon atoms is between 12 and 14 are preferably used.

According to the invention, it is preferable if η in the alkylene oxide chains is 2, 3 or 4, and it is particularly advantageous if η is 2.

When a primary amine compound with a long aliphatic chain with an alkylene oxide reacts, whereby a tertiary amine is formed, their properties change such that it is suitable for preventing the "milkiness" of a thread and the clogging of the spinneret holes or to diminish them. By regulating the chain length of the alkylene oxide derivatives can be obtained which are soluble in both viscose and acidic spinning baths are stable. The required length of the alkylene oxide chain is dependent on the alkyl groups of the amine dependent, since the alkyl group becomes more hydrophobic as the chain length increases while on the other hand, the alkylene oxide chain becomes more hydrophilic as the chain length increases. 6g It is therefore only necessary to adjust the length of the alkylene oxide chain so that this dominates the alkyl group in the amine, whereby the ■ condensation product becomes sufficiently water-soluble, to be effective for the required purpose.

The compounds described above are sold under the trade name "Ethomene" in the Trade brought. These compounds are reaction products of primary amines with a long aliphatic chain and ethylene oxide. The reaction is usually illustrated as follows:

RNH ₂ + (x + y) G _n H _8n O - »-

"(C _n H _2n O) ^ H

In this structural formula, R can be an aliphatic chain with 8 to 24 carbon atoms in the molecule, and a chain with 12 to 14 carbon atoms in the molecule is preferably used. The value of χ or y is at least 1, and in total the number of alkylene oxide chains (x + y) in the compound should be at least 5. There is no upper limit to this number, although 12 to 18 or about 15 is the desired number. Preferably, η is between 2 and 4.

Special "ethomene" which are very effective in avoiding "milkiness" and growth of spinneret holes are "Ethomen C / 25" and "Ethomen S / 25".

Schematically, the reaction ratio for these two compounds can be given as follows will:

RNH ₂ + 15 (C ₂ H ₄ O) - + - RN:

, (C ₂ H ₄ O) _x H.

Coconut oil (C / 25) or soybean oil (S / 25) is used to produce the amines, and this determines the length of the aliphatic chain of R. In the two compounds the molecule after the reaction with ethylene oxide comprises 15 molecules of this latter compound. When the tertiary amine is formed, the ethylene oxide appears to be! split into two chains, denoted by χ and y, depending on the circumstances. It has been found that ethylene oxide is more attracted to nitrogen than to the hydroxyl group, so that a bishydroxyethylalkylamine is formed. After a total of 5 molecules of ethylene oxide was added to the primary amine, it was found that 99% of it was converted to a tertiary amine. Theoretically, the reaction product can therefore contain at least 5 molecules of ethylene oxide, provided that it is sufficiently soluble in alkali and acid. For best results, however, is

an amount of about 15 ethylene oxide molecules per amine molecule is required for the reaction.

According to the invention, the long chain-like condensation product of the aliphatic tertiary Amine alkylene oxide in smaller amounts, for example 0.12 to 0.24%, calculated on the weight the cellulose, the viscose and, if necessary, added in smaller quantities to the acidic spinning bath, taking the necessary care, of course

Maintaining an even mix must be taken. In practice it has been found that it is particularly advantageous if the condensation product is added in a preliminary stage will, e.g. B. during grinding. The alkali cellulose seems to loosen up as a result, what has the consequence that the subsequent effects can take place better.

After adding the condensation product, the viscose is prepared in the normal way, whereupon it is deformed in the usual way.

Tests have shown that the condensation product in terms of prevention the "milkiness" has a greater effect than the highly sulfonated, non-mineral oils, which are marketed under the name "Praestabit oil". Even when in use a five times greater amount of the latter oil the results obtained were no better than with the application of the product according to the invention.

In addition, the condensation product was very effective in preventing the Overgrowth "of spinnerets, while the highly sulphonated, non-mineral oil this problem does not overcome. With regard to the solubility and stability of Bishydroxyäthylalkylamine, those using amines from coconut oil (»Ethomen C / 25«) or soybean oil (»Ethomen S / 25 «), attempts have been made by dissolving in cold and boiling acid as well as employed in cold liquor. It was resolved to 2% of the "ethomene" and the results were as follows:

Bis-hydroxyethylalkylamine

("Ethomen") 2%
Ethylene oxide solution.

and
Coconut oil (C / 25)

5% acid

cold

clear

Soybean oil (S / 25) clear clear clear clear

dend

clear

6% NaOH

cold

clear

24 hour storage

clear

From the above it follows that the. named compounds in the two media are sufficiently soluble and stable.

These viscoses were at a normal maturity of 9.8 and at a higher maturity (11 to 11.5) spun in the normal way according to Hottenroth. Upon observation, it was found that the final product of the same quality or even better than rayon, which is highly sulfonated, was not mineral oil ("preastabit oil") was added to the viscose used in their production.

If the additive used according to the method is in the amounts of viscose specified above is added and the viscose was in an acidic, non-cationic containing agent Spinning bath, it was found that the pressure on the spinneret was significantly reduced. This means a thorough prevention of the clogging of the spinneret holes, what was confirmed by microscopic examination of the spinneret holes.

It is evident that the use of smaller amounts of long chain-like condensation products of aliphatic tertiary amine ethylene oxides according to the invention in the production artificial structure made of viscose brings several significant advantages.

Claims (5)

PATENT CLAIMS: i. Process for the production of artificial structures such as threads or films Viscose, in which a cation-active compound is used, characterized in that that a cationic compound is the formula -R ₂ is used, in which R _{1 is} an aliphatic hydrocarbon chain with at least 8 carbon atoms in the molecule and R ₂ and R _{3 are} alkylene oxide chains, which are represented by - (C _n H _2n O) a H, in which χ for R ₂ and R ₃ can be different, but in such a way that in any case the total number of groups of R ₂ and R _{3 is} at least 5 and χ can not be zero in either of the two. 2. The method according to claim 1, characterized in that the aliphatic chain of R _{1 contains} 8 to 24, preferably 12 to 14 carbon atoms in the molecule. 3. The method according to claim 1 or 2, characterized in that η in the alkylene oxide chains is 2, 3 or 4 and is preferably equal to 2. 4. The method according to any one of the preceding claims, characterized in that η in the alkylene oxide chains is equal to 2 and that the number of ethylene oxide groups in the cation-active compound is a total of about 15. 5. The method according to any one of the preceding claims, characterized in that the Amount of the cation-active compound added to the viscose 0.12 to 0.24%, calculated on the cellulose weight. Considered publications: German patent specifications No. 696 780, 667 744. 1 609 715 12.56