DE914306C - Mixture for the production of dyeable threads or fibers - Google Patents

Description

(WlGBl. P. 17S)

ISSUED JULY 1, 1954

M8694IV'c 129b

The invention relates to new and valuable mixtures, mainly of acrylonitrile polymers, those in the deformed state by conventional methods especially with acidic dyes can be colored.

The mixture which contains 6o to 98% of a polymer consisting of at least 75% of acrylonitrile consists, and moreover 2 to 40% of a polymer of vinyl pyridine or alkyl-substituted Having vinyl pyridines, the pyridine nuclei by reaction with an alkyl ester Sulphonic acid has been made quaternary, meets this requirement.

It is well known that polyacrylonitrile and copolymers of acrylonitrile and other monoolefinic polymerizable monomers excellent thread-forming copolymers are. Polyacrylonitrile and mixed polymers with over 75% acrylonitrile and one Content of monomers up to 25%, e.g. B. vinyl esters ao of monocarboxylic acids, alkyl methacrylates, vinyl-substituted aromatic hydrocarbons, vinylidene chloride and methacrylic acid nitrile, produce threads, which have excellent strength properties and which have sufficient elongation and excellent Show resistance to physical and chemical stresses. These However, polymers and the filaments produced from them have disadvantages which affect their usefulness restrict e.g. B. these threads do not have sufficient affinity for dyes.

It has been found that common thread-forming acrylonitrile polymers or copolymers of acrylonitrile and other polymerizable

Monoolefin monomers (first component) can thereby be made dye-receptive, that they are mixed with polymers of olefinic compound (second component), the at least one contain heterocyclic ammonium group.

Copolymers of acrylonitrile are particularly suitable as the second mixed component those of the part having a heterocyclic nitrogen ring by reaction with alkyl esters ίο have been made quaternary by oxygen-containing sulfonic acids,

Acrylonitrile polymers (first component), which according to the invention are to be made capable of absorbing dyes, are polyacrylonitriles and copolymers which consist of 75 or more percent acrylonitrile and up to 25% of other monomers, such as vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, ethyl methacrylate, Methyl aerylate, ethyl acrylate, styrene, α-methyl styrene, vinyl diphenyl, isopropenyl, diphenyl, dimethyl fumarate, dimethyl maleate, diethyl maleate, diethyl fumarate, vinylidene chloride and methacrylic acid nitrile. According to the invention, polymers of vinyl pyridine or any alkyl-substituted pyridines which have a vinyl substituent on one carbon atom of the ring and which have been made quaternary are used as the second component of the mixture. Usable vinyl pyridines are: 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 2-vinyl-4-ethylpyridine, 2-vinyl-3-methylpyridine, 5-vinyl-2-methylpyridine, 2-vinyl - 5 - ethylpyridine, 2- Vinyl-4-methylpyridine, 3-vinyl-5-ethylpyridine and other alkyl-substituted vinylpyridines in which the alkyl radical contains 1 to 4 carbon atoms. Copolymers of these vinyl pyridines and in particular the acrylonitrile copolymers are to be preferred. The copolymers can contain up to 80% acrylonitrile and the remainder can consist of vinyl pyridine. Mixtures which have significant proportions of acrylonitrile are preferred, e.g. B. 30 to 70 ⁰ Zo, with which a better solvent resistance is achieved. The polymers are made quaternary by reaction with alkyl esters of sulfonic acids. The vinyl pyridines are reacted with the alkyl esters of sulfonic acids and then they can be polymerized or copolymerized with acrylonitrile.

The mixed polymer (second component) from Acrylsäurenitrilund vinylpyridine be converted inquaternäre ammonium derivatives characterized in that they are reacted with alkyl esters of acids of sulfur, the ionization must be less than 10- ⁴ (z. B. with sulfuric acid, sulfurous acid / toluene sulfonic acid, benzenesulfonic acid and other alkyl, aryl, aralkyl and alkaryl sulfonic acids), The reaction with the quaternizing agent need not be complete, but the color receptivity of the copolymer is better when the quaternization is complete. Accordingly, 5 to 100% of the theoretically required amount of the quaternizing agent can be added.

In order to have a useful dye uptake ability of the products made from the mixture achieve, the total vinylpyridine content of the second components of the mixture should be 1 to 15% the optimal content is 2 to 10%.

The monomers with the copolymers forming the main constituent or with the additives Mixed polymers can form useful mixed polymers j (first component) are styrene, ! α-methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic acid nitrile, methacrylic acid nitrile, Acrylic acid, methacrylic acid, maleic anhydride, alkyl acrylates, alkyl methacrylates, vinyl esters, alkyl crotonates, Alkyl maleates, alkyl fumarates, butadiene, isoprene and chloroprene.

In practicing the present invention the mixtures that can form dyeable fibers or threads are made by mixing the solid resins in suitable customary mechani-; see mixing devices manufactured, e.g. Am ; Mixing devices with counter-rotating impellers, in ball mills or in dough mixers. It's general desired, suitable solvents or plasticizers for the fiber-forming acrylonitrile to add polymers. Suitable solvents for acrylonitrile polymers are, for example N, N-dimethylformamide, N, N-dimethylacetamide, Butyrolactone, ethylene carbonate and N, N-dimethylmethoxyacetamide, these are also solvents for the various additional resins that are used in accordance with the process be used. Mixtures of 2 to 40%) of the additives described above (second component) and from 60 to 98% of the acrylonitrile fiber-forming polymer (first component) for the production of valuable synthetic threads or fibers, which have an optimal dye absorption capacity, useful.

The new mixtures are made synthetic by conventional wet or dry spinning processes Threads processed. After drawing the filaments of the mixed acrylonitrile polymers to the Increased strength is then caused by heat to shrink the threads to improve their resistance to elevated temperatures.

Example 1 _ijo

After mixing together 637.5 g of N, N-dimethylacetamide and 7.9 grams of methyl p-toluenesulfonate 103.5 g of finely divided copolymer of 95% acrylonitrile and 5% vinyl acetate (first Component) and 9 g of finely divided copolymer of 50% aeryl acid nitrile and 50% vinyl pyridine (second component) was added and the mixture was stirred at 80 ° for 1 hour. Man received a clear homogeneous solution. The temperature was then lowered to 65 ° and thereby Held for 12 hours to complete the quaternary reaction.

The solution was then passed through a spinneret that had thirty openings, each 1.25 mm in diameter had, squeezed into a spinning bath, which consists of 60 parts of N, N-dimethylacetamide and 40 parts of water

was standing. The threads were drawn 600%, washed and dried.

The threads exhausted a dye bath which was made up of ι ecm of a 2% aqueous solution of CI-252 [Wool Fast Scarlet G Supra, Concentrated (manufacturer: Geigy)], 5 ecm 3% sulfuric acid and 40 ecm of water existed for every 1 g of the thread to be dyed.

Example 2
10

It was worked in the same way as in the previous example, except that 5% of the stoichiometric proportion of methyl p-toluenesulfonate is used instead of a 100% and 99.5 g of the copolymer of 95% acrylonitrile and 5% vinyl acetate (first component) and 13 g of copolymers of 30% acrylonitrile and 70% vinyl pyridine (second Component) have been applied. The polymeric solution was then prepared that first the Mixed polymers with 30% acrylonitrile and 70% vinylpyridine in N, N-dimethylacetamide with ordinary Temperature was dissolved and then the methyl p-toluenesulfonate was added, whereupon Was heated for 12 hours to produce the quaternary compound. After cooling down the copolymer of 95% acrylonitrile and 5% vinyl acetate in the Dispersed solution, which was then heated to 8o ° for 1 hour and a clear and homogeneous Solution resulted.

The threads were spun in the manner described above (see the previous example) and colored, whereby the dye bath was completely exhausted.

Example 3

The procedures according to Example 2 were repeated, except that 7.9 g of methyl p-toluenesulfonate were used (50% of the stoichiometric proportion) were applied. Those made in the usual way Threads showed good dye absorbency, so the unit dye bath accordingly Example 1 has been exhausted.

Example 4

A mixed solution of polymers was prepared from 106.1 grams of a mixed polymer of 95% acrylonitrile and 5% vinyl acetate (first component), 6.4 g of a copolymer of 30% Acrylonitrile and 70% vinyl pyridine (second component), 637.5 g of N, N-dimethylacetamide and 7.9 grams of methyl p-toluenesulfonate. The implementation of the reacting substances and the conversion into the quaternary ammonium salt was effected in the manner described in Example 2. From it The threads produced exhausted the dye bath and showed outstandingly saturated colors.

Example

Using the procedure described in Example 2, there was 109.3 grams of an interpolymer of 95% acrylonitrile and 5% vinyl acetate (first component) with 3.2 g of a copolymer of 30% acrylonitrile and 70% vinyl pyridine (second component) in 637.5 g N, N-dimethylacetamide mixed. To make the quaternary connection, one used 4.2 grams of methyl p-toluenesulfonate. The threads were dyed with exhaustion of the dye bath. 70 '

Example 6

A solution of polymers was prepared by dispersing 13.8 g of a finely divided polymer Polymers with 95% acrylonitrile and 5% vinyl acetate (first component) and 1.3 g finely divided Polyvinylpyridine (second component) was added to 85 g of N, N-dimethylacetamide, which had previously been mixed with 2.2 g of methyl p-toluenesulfonate.

This solution was through a spinneret with ten openings, each 0.126 mm in diameter a mixture of water and N, N-dimethylacetamide pressed. The thread could after known Procedure to be easily colored.

Example 7

A solution was prepared by following the procedure of the previous example, yielding 637.5 g N, N-dimethylacetamide, 7.9 g methyl p-toluenesulfonate, 90 g of a copolymer of 95% acrylonitrile and 5% vinyl acetate (first component) and 22.5 g of a copolymer of 80% acrylonitrile and 20% vinyl pyridine (second component) were used. Filaments made by the method described in Example 1 had a excellent dye absorbency.

Example 8

85 g of N, N-dimethylacetamide were added with 1.8 g Diethyl sulfate mixed and then a mixture of 12.6 g of a copolymer of 95% acrylonitrile and 5% vinyl acetate (first component) and 2.4 g of a copolymer of 50% acrylonitrile and 50% vinyl pyridine (second component) added. The mixture was within ι hour a homogeneous solution and was then heated for 16 hours to the formation to support the quaternary connection. Threads emerging from a spinneret by pressing Spun in a spinning bath of water and N, N-dimethylacetamide had excellent results Dye receptivity.

Claims (2)

Patent claims: i. Mixture, from which easily dyeable threads and fibers can be made, thereby characterized in that the mixture of 60 to 98% of a polymer with a content of at least 75% acrylonitrile (first component) and from 2 to 40% of a polymer of vinyl pyridine or alkyl substituted vinyl pyridines (second component) consists in which the pyridine cores by reaction with an alkyl sulfonate or sulfuric acid ester, such as methyl p-toluenesulfonate or dimethyl sulfate, made quaternary. 2. Mixture according to claim i, characterized in that the second mixed component, which is 2 to 40 ⁰ Zo, consists of a copolymer of 30 to 70% acrylonitrile and 70 to 30% of vinyl pyridine or alkyl-substituted vinyl pyridine, in which the pyridine groups by reaction have been made quaternary with an alkyl sulfonate. I 9524 6.54