DEC0004975MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: November 14, 1951. Advertised on December 15, 1955

GERMAN PATENT OFFICE

This invention relates to novel dyeable fiber-forming compositions made from, in particular, acrylonitrile polymers, which are colored by known methods, in particular with acid dyes be able.

It is known that polyacrylonitrile and copolymers of acrylonitrile with other monoolefinic polymerizable monomers are excellent fiber-forming copolymers. The polyacrylonitrile and copolymers of more than 75% of acrylonitrile and up to 25 ° / ₀ of an other polymerizable monomers yield fibers with superior stretch characteristics, desirable elongation at break and excellent resistance to physical and chemical respects. However, these polymers have disadvantages which limit their usability in manufacture very much. Such fibers have such. B. insufficient dye affinity, and applied dyes were found to be incorrect in laundry and dry cleaning processes.

It has been found that non-dyeable fiber-forming polymers and copolymers of the heretofore Kind of like polyacrylonitrile and mixed polymers

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() ;, ",, Acrylsäiirenilril and 5" Z ₁₁ vinyl acetate, can be brought into a colorable form by incorporating certain amounts of N-yinylimidazole polymers.

The acrylonitrile polynes produced by the previous processes, which are obtained by incorporating N-vinylimidazole polymers can be modified, are polyacrylonitrile and mixed polymers of 75 or more percent acrylonitrile and up to 25% on monomers such as vinyl acetate and other yinyl esters of monocarboxylic acids with up to 4 carbon atoms, methylniethacrylate and other alkyl methacrylates, Mclhylaerylat and other alkyl acrylates, dialkylfuinaraten and Dialkyhnaleates, in all cases with up to 4 ('atoms in the alkyl groups, styrene, «-Methylstyrene and others by vinyl or isopro |) enyl substituted aromatic hydrocarbons, Vinyl chloroacetate and other vinyl esters !! from ha logt'Hsu to allied acetic acids, vinylidene chloride

so and Methylaerylsäiirenitril. These polymers and Copolymers themselves are generally difficult to dye.

The new, dyeable fiber-forming compositions contain a mixture of 70 to C) (S ⁰ Z _{n of} a polymer of 75 to 100% acrylonitrile and ο to 25 "/ ,, of another polymerizable olefinic monomer, such as vinyl acetate, with 2 to 30 ⁰ Z _{0 of} a second polymer composed of 30 to 100 "/" N-vinylimidazole and ο to 7ο ⁰ / "of another polymerizable olefinic monomer, such as acrylonitrile.

In practicing this invention, the N-vinylimidazole polymers are prepared separately and intimately mixed with the non-dyeable acrylonitrile polymers. The resulting Mixed breeds can be spun into fibers by known processes, while those with acid dyes are known Process are easy to color.

The polymers of N-vinylimidazole can be the homopolymer « ¹ or the copolymers of

4 »N-Vinylhuida / .ols with a large number of olefinic Monomers that can be mixed polymerizable with it, (ie suitable monomers for carrying out this Polymerization are styrene, «-methylstyrene, vinyl chloride, Vinylidene chloride, vinyl acetate, acrylic acid, methacrylic nitrile, acrylic acid, methacrylic acid, Maleic anhydride, the alkyl acrylates, the alkylin ethacrylates, vinyl ethers, the alkyl crotonates, the Alkyl maleates, the alkyl fumarates, butadiene, isoprene and ('hloi'iipi'en. Since the copolymers of N-vinylimida / .ol and acrylic acid nitride has good properties in terms of heat resistance and insolubility, they are preferred. The mixed polymers are added in such proportions as 1.1 N-yinylimidazole .; to 15 "/ ,, of the total monomers in the Composition matters.

The polymers and copolymers of N-Vinyliniida / .ols can by the various known methods by polymerization in bulk, in Solution or in emulsion. A

<io preferred polymerization process uses the Reaction in an aqueous medium in the presence of suitable 1) ispergiennit (el and suitable free radicals generating catalysts.

In the preparation of the mixed emulsion polymers of N-vinylimidazole, it has been found that a A variety of emulsion stabilizers can be applied; with the alkali salts of formaldehyde-naphthalenesulfonic acid condensation products and various alkali salts of fatty acids and fatty acid mixtures were found to be unusually successful work. Various peroxides, both oil- and water-soluble types, can be used as catalysts as well as azo derivatives are used. The preparation of the emulsion copolymers described here is not claimed.

Then non-dyeable fiber-forming polymers can be used and the N-vinylimidazole polymers are mixed by any conventional mixing machine. Although the mixing can take place at elevated temperatures at which the polymers become soft or semi-liquid state, it is better to add suitable solvents or plasticizers, to be able to mix at low temperatures. Suitable solvents for mixing the acrylonitrile polymers with the N-vinylimidazole polynes are N, N-dimethylformamide, N, N-dimethylacetamide, «-Butyrolactone, ethylene carbonate and N, N-dimethylmethoxyacetamide. In general result in 50 to 90 ° / ,, of the solvent the desired semi-liquid or soft state.

In the production of the copolymers depends on the; Amount of Each Component of the Mile "; on N-vinylimidazole desired in the final composition and the level of N-vinylimidazole in the N-vinylimidazole polymer. in the 2 to 30% of polymerization products are generally used; λ-οη N-vinylimidazole and 70 to 98 ° / ,, des non-dyeable polymer comprising 75 to 100% acrylonitrile.

The masses are converted into synthetic fibers by the usual wet and dry spinning processes. The threads obtained from the mixed acrylonitrile polymers are stretched and post-treated in a known manner.

B ei s] i i el 1

A mixture of 70 g of acrylonitrile with 70 g of N- \ ^T inylimidazole was mixed with 1 percent by weight of azodiisobutyronitrile and the resulting mixture was added over 1.2 hours to 800 g of water containing 4 g of sodium stearate and 2 g of the sodium salt of the formaldehyde-naphthalenesulfonic acid condensation product. During de r throughout the polymerization, the reaction mixture was maintained at 83 "After the whole Me;. Nge had been added to the monomers, the mixture was steam distilled to remove unreacted monomers to remove the material was dried overnight at 70 ⁰ gc dried and then. dissolved in N, N-dimethylacetamide to a 24% solution.

This solution was mixed with an i8 ° / ₀ aqueous solution of a polymer consisting of 97% acrylonitrile and 3 ° / "vinyl acetate, also in N, N-Dimethylacctamid. Sufficient vinyl acetate copolymer was added to obtain a solution of the copolymer in which N-vinylimidazole was 6.6 ° / ₍ , des

590 / 1.19

Claims (1)

C 4975 IVc / 29b Solid polymers. The solution obtained in this way was spun into fibers which had a strength of 4.5 g / denier, an elongation of 6 ° / ₀ and a boiling shrinkage of 10.4%. Example 2 Following the procedure described in the previous example, a number of mixtures of the Weight percent
N vinyl
imidazole Dope
concentration Grams /
denier 0 to 25% of a Stretch values 0 /
/ 0
Koeh-
shrinkage fracture
strain 30 to 100 ° / ₀ N-vinylimidazole 6.4 4.5 5.55 10.4 6th of another polymerizable 3.8 3.5 3.78 8.6 7th olefinic monomer, such as Acrylonitrile, i5, i 3.3 4.97 10.3 7 to 8 contains. 5, o 4, o 4.64 8.0 6th 18.1 other polymerizable olefinic monomer,
like vinyl acetate, and 2 to 30% of a second 15.1 for the production of dyeable Polymers from 18.7 marked that they are a and 0 to 70% 17.0 up to 98% of a polymer PATENT CLAIM: 75 to 100% acrylonitrile and Spinnable mass Fibers, thereby Mix of 70 Mixed polymer of 97 percent by weight of acrylonitrile with 3 percent by weight of vinyl acetate and the as mixed polymer of 50 percent by weight of acrylonitrile with 50 percent by weight of N-vinylimidazole. The ones spun from each of these blends
Fibers were dyeable and had the following
Features: 30 © 509 599/149 12.55