DE1243818B - Process for the production of threads or foils from regenerated cellulose - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

DESIGN SCREEN

Int. Cl .:

DOIf

German class: 29 b - 3/20

Number: 1 243 818

File number: F 38221IV c / 29 b

Filing date: November 3, 1962

Opened on: July 6, 1967

It is already known to produce shaped structures, such as threads or films, from regenerated cellulose, by adding compounds of various chemical structures to the viscose or its preliminary stage and / or to the acidic precipitation bath. Through the The addition of these compounds generally improves the spinnability and clarification of the viscose, the clogging of the spinnerets is reduced and an increased swelling of the threads in the acidic spinning bath causes. However, the known additives have the disadvantage that to achieve the desired structural properties the electrolyte concentrations in the acidic spinning bath are kept in narrow and low ranges Need to become. Since adhering to these concentration ranges is laborious, step with the known Modifying agents, e.g. B. oxäthylierten Fettaminen, easy difficulty in spinning or in the Stretching of the spun structure, which can also be achieved by adding polyglycols or alkali salts of sulfonated lignin cannot be completely eliminated.

The subject of the invention is a method for producing threads or foils by spinning of viscose, which contains a nitrogen-containing compound with sulfonic acid groups as a modifying agent, in common acidic precipitation baths. It is characterized by that a viscose is spun that contains water-soluble organic sulfamides as modifiers, which contain at least one basic aminoalkyl group, the hydroxyalkyl groups on the nitrogen and / or polyglycol ether chains, and which at least one branched or un-process for the production of threads or foils from regenerated cellulose

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning, Frankfurt / M.

Named as inventor:

Dr. Ludwig Orthner, Frankfurt / M .;

Dr. Martin Reuter, Kronberg (Taunus);

Dr. Franz Landauer,

Frankfurt / M.-Unterliederbach

branched aliphatic or cycloaliphatic hydrocarbon radical have medium or higher molecular weight.

The addition of the modifying agent used according to the invention can also be carried out at a preliminary stage of the Made of viscose. The additives which can be used according to the invention essentially correspond to the general ones formula

RSO ₂ - N (Z) - (C «H _am ) ~ N - (Z) ₀ - [(C _m H _2W ) - N (Z) J ₆

wherein R is optionally interrupted by heteroatoms or heteroatom groups branched alkyl radical of the underlying alkyl sulfonic acid, Z is hydrogen and a total of at least two hydroxyalkyl radicals

- CjiH ₂ n + i- i (OH) i

or polyalkylene ether chains
- [C _n H ₂ η -

where η and y are at least 2 and χ are at least 1, but, χ and y can also be higher numbers and the straight-chain or branched alkanol radical C _{n can} also be interrupted or substituted by heteroatoms or heteroatom groups and optionally also hydrogen and / or alkyl radicals and / or remains of the constitution

Q _n H _27n - N (Z).

m can be 2 or higher numbers and the remainder C _{m of} aliphatic or cycloaliphatic nature and can be substituted by heteroatoms or heteroatom groups, a is 1 or 2 and b is numerical values from 0 to 4. Advantageously, the sulfamide on which it is based is not terminally substituted in the radical R, but rather substituted in the chain, e.g. B. derived from the sulfochlorination of hydrocarbons according to Reed.

709 609/417 '

The additives which can be used according to the invention can be prepared by known methods. For example, compounds of the following constitution are suitable:

a) C ₁₂ H ₂₅ SO ₂ NH

CH ₂ OH

C ₂ H ₄ - N - C - C - CH ₂ OH
H j

CH ₂ OH

b) C ₁₂ H ₂₅ SO ₂ NH-C ₂ H ₄ -N:

. C ₂ H ₄ OH

^N C ₂ H ₄ OH

, CH ₂ - CH _{2 χ}

c) C ₁₈ H ₃₅ SO ₂ NH - C ₂ H ₄ - N '

....... .... X ρττ / " ¹ XJ

^ n ₂ --- ν ^ -Π ^
CH ₂ OH

d) C ₁₈ H ₃₅ SO ₂ -NH-C ₂ H ₄ -NH-CH

(CH0H) _P
CH ₂ OH

N - C ₂ H ₄ OH

e) C ₁₂ H ₂₅ SO ₂ -NC ₂ H ₄ -

^j C ₂ H ₄ OH

f) C ₁₂ H ₂₅ SO ₂ - NH-C ₂ H ₄ ■

N - C ₂ H ₄ - N C ₂ H ₄ OH
-NH- C ₂ H ₄ -

. C ₂ H ₄ OH

C ₂ H ₄ OH

NH - CH ₂ - CH - CH ₂ OH OH

g) CH,

, CH ₂ - CH ₂

CH CH

^{2 2}

: CH - SO ₂ - N - C ₂ H ₄ - N - C ₂ H ₄

C ₂ H ₄ OH, C ₂ H ₄ OH. C ₂ H ₄ OH

NC ₂ H ₄ OH C ₂ H ₄ OH

h) CH ₃ - SO ₂ - N - C ₆ H ₁₂ - N:

C ₂ H ₄ OH

C ₂ H ₄ OH

If necessary, no precipitates can form in these compounds with the addition of the sulfamide

for the purpose of better solubility in water still through conversions and settlements in the spinning apparatus, while without

Settlement with about 2 to about 20 moles of ethylene oxide causes the addition considerable difficulties due to low

Existing longer polyglycol ether chains are introduced and deposits occur. The number of

will. : r: torn element threads are indicated by the addition

. ■■ ·.:;: · '_ Tend decreased. When spinning the SuIfamid

: Example ₅₅ containing viscose high-strength threads are obtained:

; ' The threads obtained with the addition are round

Among the same commonly used full jacket structure with smooth outline shape.

Spinning conditions are viscose with and without additives. The sulfamide used as a modifier

of 2 g / l of the sulfamide based on a diesel oil fraction was obtained in the following way:

tion, the preparation of which is described in more detail below 60 1 mole of an aliphatic sulfochloride with a

is, through fine-perforated noble metal nozzles in a 6O ⁰ C. average chain length of 18, carbon:

spun in a warm spinning bath, which contains 63 g / l sulfur atoms, which is produced by sulfochlorination according to Reed

acid, 60 g / l zinc sulphate and 165 g / l sodium sulphate and the carbon which has not yet been sulphochlorinated

holds. In a second, weakly acidic, 92 ° C hot hydrogen, according to Schotten -

In the bath, the threads are stretched by 100%. Without the 65 Baumann with 1 mole of tetrahydroxyethyl diethylene

According to the invention: Additives clog the spinning holes: triamine in the presence of molar amounts of sodium hydroxide solution

after a few hours of work, when using the (25%) implemented. After separating from the neutral oil

Sulfamides, the spin holes remain open. Furthermore, which comes from non-de-oiled reed sulfochloride,

the reaction product was evaporated. The sulfamide of tetrahydroxyethyl diethylenetriamine formed was freed from sodium chloride by digestion with alcohol. The water-soluble product is readily soluble in a 50-fold amount of normal viscose of 6.4% cellulose, 5.4% sodium hydroxide solution and 38% CS ₂ .

An equally good product is obtained if 10 or 25 mol.; Ethylene oxide are deposited in the presence of alkaline catalysts.

An equally effective viscose modifier is obtained when using instead of a sulfochloride with an average chain length of 18 carbon atoms, a sulfochloride prepared according to Reed with an average chain length of 12 carbon atoms used for the Schotten-Baumann reaction will.

Claims (1)

Claim: Process for the manufacture of threads or films by spinning viscose, which is a nitrogenous Contains compound with sulfonic acid groups as a modifier, in common acidic precipitation baths, characterized in that a viscose is spun as a modifier water-soluble organic sulfamides containing at least one basic aminoalkyl group, which carries hydroxyalkyl groups and / or polyglycol ether chains on the nitrogen atom, and which at least one branched or unbranched aliphatic or cycloaliphatic hydrocarbon radical have medium or higher molecular weight. Considered publications:
German publication No. 1130 962.