DE1267424B - Improvement of the colorability of acrylonitrile polymers compared to basic dyes - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German class: 39 b -22/06

Number: 1267 424

File number: P 12 67 424.7-43

Filing date: August 26, 1963

Open date: May 2, 1968

It is known that aeryl nitrile polymers generally have a low absorption capacity have basic dyes. Therefore, there is an improvement in the dyeability of acrylonitrile polymers poses a particular technical problem.

There are various polymers to improve the colorability compared to basic Dyes Compounds containing sulfonate groups which are copolymerizable with vinyl compounds have been used.

So the dyeability of acrylonitrile z. B. by copolymerization of acrylonitrile with a number of sulfonated vinyl aromatic compounds. For example were sodium p-methacrylamidobenzene sulfonate, aromatic alkenyl sulfonic acids or their salts are polymerized with various acrylonitrile monomers to form dyeable polymers, Copolymers and polymer mixtures for the production of fibers, threads or films to obtain.

These known derivatives of unsaturated sulfonic acids that improve the colorability of acrylonitrile polymers come into consideration, but are only possible via those carried out in the laboratory Syntheses available, in which case relatively expensive starting materials often have to be used. Therefore, their use to improve the dyeability of acrylonitrile polymers is against subject to considerable technical restrictions via basic dyes.

A process for improving the dyeability of wet-spun and stretched threads or fibers made from polymers and copolymers of acrylonitrile containing at least 85 percent by weight of acrylonitrile in the polymer molecule is also known from German Auslegeschrift 1,083,492. In this method structures are, while they are in the form of a hydrogel and shrinkable condition, brought at a temperature between 95 and IOO ⁰ C temperature for 2 to 30 seconds with an aqueous flash liquid into contact, a surface tension of not more than 30dyn / cm ² .

This is a relatively complicated procedure, in which the fibers or threads have to be brought into contact with an aqueous hot relaxation liquid with a particular surface tension in a separate step, with particular working conditions improving the dyeability of
Acrylonitrile polymers versus basic ones
Dyes

Applicant:

Monsanto Company, St. Louis, Mo. (V. St. A.)
Representative:

Dr. E. Wiegand and Dipl.-Ing. W. Niemann,
Patent attorneys,

8000 Munich 15, Nussbaumstr. 10

Named as inventor:
James Carter Masson,
Chapel Hill, N. C (V. St. A.)

Claimed priority:

V. St. v. America dated August 27, 1962. (219 760)

are to be held. The deviations from the usual associated with this known mode of operation Process for the production of threads and fibers and other structures from acrylonitrile polymers are technically disadvantageous, since this involves an increase in the expenditure of time and, accordingly, a Reduction of the production output is connected, in addition, the risk of impairment of the Product quality exists if the working conditions are not carefully regulated.

Furthermore, from the German Auslegeschrift 054 656 a method for the production of threads is or fibers made from polyacrylonitrile and / or its copolymers with good coloring properties known. In this process, a solution is spun which, in addition to polyacrylonitrile and /

809 574 433

Claims (1)

or its copolymers containing starch cyanoethyl formula ether, which is insoluble in water, but in the organic solvent is soluble. According to this procedure, 10 parts by weight of starch cyanoethyl ether are added to 90 parts by weight of polyacrylonitrile 5 used. This process is obviously disadvantageous in that, on the one hand, the high additional amount required increases costs and what is more, the acrylonitrile polymers or copolymers desired mechanical properties are impaired to an undesirable extent. The object of the invention is to improve the colorability of acrylonitrile polymers compared to basic dyes with the aid of an agent when using it, there is no fundamental deviation from the usual manufacturing process of the acrylonitrile polymer products is required and that does not impair the advantageous and desired properties of the acrylic nitrile polymers and is also available in a simple manner on an industrial scale. It has been found that the use of alkali allyloxybenzenesulfonates of the general SO ₃ Y R ' O-CH-C = CH ₂ R in which R and R 'are hydrogen, methyl, ethyl or propyl and Y is an alkali metal, the The colorability of acrylonitrile polymers is significantly improved compared to basic dyes can be without adversely affecting the good mechanical properties of the objects produced from the acrylonitrile polymers will. The alkali allyloxybenzenesulfonates to be used according to the invention can be various Ways to be produced according to known analogy processes. They become particularly beneficial after one Method that is represented by the equation below: SOrY ⁺ + 2 H ₂ O + NaOH + CH ₂ = C - CH - X R ' OH SO ₃ -Y ⁺ + NaX + 3H, 0 in which R and R 'are hydrogen, methyl, ethyl or propyl, X is chlorine, bromine or iodine and Y is Alkali metal, e.g. B. represents lithium, cesium, sodium, potassium or rubidium. The compounds used according to the invention can also have a meta or ortho orientation. The preparation of the alkali allyloxybenzenesulfonates according to the invention to improve the Colorability of polyacrylic polymers are used, is simple and can easily be im technical scale. The alkali allyloxybenzenesulfonates used according to the invention are general as receptors or absorbent substances for basic dyes can be used in all types of acrylonitrile polymers. example Sodium methallyloxybenzenesulfonate was acrylonitrile in various amounts. as in indicated in the table below, and the basic dye uptake was determined. The results obtained are summarized in the table below. Dye absorbency of modified with sodium methallyloxybenzenesulfonate Acrylonitrile polymer versus basic dyes Nsp-
viscosity Weight percent
Acid monomer BDA BDE
End groups BDA
Acid monomer BDA (weight percent)
Acid monomer Average 0.170 0.5 19.0 10.5 8.5 17.0 0.168 0.5 18.8 10.6 8.2 16.4 0.151 0.4 17.0 11.8 5.2 13.0 15.4 0.192 0.3 13.8 9.3 4.5 15.0 BDA = basic dye uptake.