DE975601C - Process for the production of copolymers of acrylonitrile - Google Patents

Description

ISSUED FEBRUARY 8, 1962

F 102/8 IV d / 39 c

Frankfurt / M.

It has already been proposed to combine acrylonitrile with chlorine-containing compounds in which at least a chlorine atom is adjacent to the polymerizable double bond, such as vinyl chloride, Polymerize vinylidene chloride, chlorobutadiene and the like.

It has now been found that halogen-containing, especially chlorine- and / or bromine-containing, not copolymerizable Alcohols, which in turn are etherified with vinyl alcohol, polymerize particularly easily with acrylonitrile and become valuable Lead products with remarkably good solubility. As chlorine-containing, not copolymerizable Alcohol components come into question z. B. ethylene chlorohydrin, i-oxy-3-chloropropane, 1,2-dioxy-3-chloropropane, i-Oxy-3-chloropropane, i-Oxy-3-bromopropane. The chlorine-containing copolymers obtained in this way can be aftertreated in various ways, once by reacting with Amines, whereby ammonium compounds are obtained. The aftertreatment of the copolymers with amines can under the known conditions in aqueous or organic phase and with all amines commonly used for aminations. You can continue with dyeing under certain conditions the chlorine can be partially hydrolyzed. The ethers containing halogens can advantageously also be used together with basic esters, ethers, sulfons or containing amino groups Hydrocarbons or amides, basic groups expediently being present in salt form, the contain a copolymerizable group, are copolymerized with acrylonitrile. Next is the interpolymerization with compounds, which

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Increasing the hydrophilicity of the polyacrylonitrile is advantageous.

As additional comonomers, the hydrophilizing have an effect, for example: vinyl acetate, diglycol monovinyl ether, allyl ethyl carbonate, Methacrylic acid glycol ester, methyl vinyl sulfone, acrylamide, methacrylamide, oxyethyl acrylamide, Allyl or methallyl alcohol.

The amount of acrylonitrile used in the polymerization must be at least 60% of that used Be monomers. However, it is preferable to work in such a way that the amount of Acrylonitrile is 80 to 95% of the amount of the monomers.

The copolymers obtained in this way can be used to form films, threads and shaped structures characterized by better coloring properties than the previously known products, processed will.

The polymerization takes place in an aqueous medium with or without emulsifiers, such as paraffin sulfonates, it being possible for salts customarily used in polymerizations to be present. The activation is made by peroxidic compounds alone or with the addition of reducing substances performed.

It is known for copolymers of acrylonitrile with vinyl chloroacetate or allyl chloroacetate after treatment with ammonia or amines products with improved colorability to obtain. However, there are limits to the choice of amines and amination conditions. since the ester group is saponified relatively easily and thus the dye-affine group is split off. Above all, it has been shown that the colorations on such aminated copolymers are not washable. Obviously, under the washing conditions, the substituted one becomes Aminoacetic acid residue is split off. The copolymers claimed here allow amination under the most varied of conditions and result in completely washfast colorations. It is also known to amine copolymers of acrylonitrile and chloro-oxy-propylallyl ether. Reworking has shown that this copolymer with dimethylformamide can be used cannot produce spinnable solutions.

example 1

The following are placed in an i-1 flask:

500.0 g water, 0.5 g glacial acetic acid.

The mixture is heated under nitrogen to remove the oxygen. Then are admitted :

90 g acrylonitrile,
10 g vinyl chloroethyl ether, ι ecm hydrogen peroxide (35%).

The polymerization is initiated by dropwise addition of 1% sodium formaldehyde sulfoxylate solution and finished. A finely powdered copolymer results. Yield 81g.

The product extracted with methanol has 3.52 and 3.43% Cl, respectively. It corresponds to a content of Vinyl chloroethyl ether of around 10%.

22.5 parts by weight of this copolymer are dissolved in 77.5 parts by weight of dimethylformamide and the solution is spun into threads in a known manner. After stretching, the material is ι at 98 ⁰ C for 1V2 hours at a liquor ratio: treated with a 5% aqueous solution of cyclohexylamine 50, then washed with hot water, then at 80 ⁰ C with 2% acetic acid or i ° / cent Hydrochloric acid acidified for 15 minutes and washed again until the rinsing water shows a neutral reaction. The silk obtained in this way has a cream-colored appearance and can be dyed with numerous acidic dyes in deep, real shades. ^{Thus, I2 fl} / o (calculated on the fiber material) are absorbed by alizarin pure blue FFB, which is dyed at the boil in excess in the presence of 4% formic acid for 1½ hours. After thorough rinsing of the fiber with cold water, the dyeing shows very good wash and lightfastness. In the same way, a deep, bright red is obtained with anthralan red G, an equally beautiful green with light green yellowish go SP and a perfect black with azo acid black 3 Bl. For other classes of dyestuff, too, the dyeability of the fiber produced according to the invention is significantly improved compared to material consisting of 100% polyacrylonitrile. For example, with nouns dyes such as Sirius red 4B and direct deep black E extra, or disperse dyes such as Cellitonech Red BB, Celliton Blue extra and Celliton black BTNU, very good colorations are obtained.

Example 2

An aqueous solution (hereinafter referred to as liquor) of the following composition is prepared:

1500 g water,

5 g sodium paraffin sulfonic acid, 30 g table salt,
5 g of magnesium sulfate-7H ₂ O.

The following monomer mixture is produced:

720 g acrylonitrile,
80 g of chloroethyl vinyl ether.

The following are placed in a 4-liter flask:

500 g liquor,

ι g hydrogen peroxide (35%), ι g glacial acetic acid,
40 g of monomer mixture.

The polymerization is allowed to take place with 40 ecm of a dilute sodium formaldehyde sulfoxylate solution (7 g sodium formaldehyde sulfoxylate in 1000 g water) start and then carry out the following three solutions in a volume ratio of 1: 1: 1

In the course of 2 hours to the reaction vessel: First, formaldehyde _{sodium sulfoxylate, 7 g in 1000 g of H 2} O, second, monomer mixture, 760 g, third, solution of 7 g of hydrogen peroxide (35%) in 1000 ecm liquor.

After the end of the polymerization, 5 g of thiourea in 20 ecm of water are added. The suspension is worked up in a known manner.

The result is a copolymer with 2.93 ⁰ Zo chlorine; this corresponds to around 9% vinyl chloroethyl ether. η _Γ (i ° Zoig in dimethylformamide): 4.6.

20 weight parts of this interpolymer are dissolved in 80 parts by weight of dimethylformamide containing 2 ⁰ Zo morpholine and heated for 2 hours at 95 ° C. The solution obtained is spun in a known manner. The fibers are washed, dried and stretched hot to a factor of oV. They have a strength of 3 ig / den. The fibers can be dyed with acidic dyes such as Alizarin Pure Blue FFB, Azo Acid Black 3 Bl, Authralan RedG, Light Green SP and Cellitone dyes.

The following information is provided for comparison:

² ^ Example 3

The procedure is as in Example 2, but the following monomer mixture is used:

720 g acrylonitrile,
80 g of allyl chloroethyl ether.

The result is a copolymer with 1.62 ⁰ Io chlorine; this corresponds to a content of allyl chloroethyl ether of 7 ⁰ Zo. The polymer yield is lower than in Example 2.

The procedure is as described in Example 2, but the following monomer mixture is used :

700g acrylonitrile,

50 g chloroethyl vinyl ether,

50 g of allyl ethyl carbonate.

The result is a copolymer with 1.53 ^fl / o Cl (around 5% v of vinyl chloroethyl ether). r / _r (i '° Zoig in dimethylformamide): 3.88.

Due to numerous attempts it has been found

that among the ethers of vinyl alcohol, allyl alcohol, Methallyl alcohol the ethers of vinyl alcohol in copolymerization with acrylonitrile best, while the ethers of crotyl alcohol polymerize the worst.

Furthermore, it has been shown that with increasing installation of the second component, the fiber properties, especially the softening point of the fiber produced from the copolymers Fibers, worsen.

Conversely, with increasing incorporation of the halogen-containing ether, the colorability decreases Amine follow-up treatment improved.

In the interests of fiber properties and the ability to be dyed, it is therefore desirable to use as much as possible use small halogen-containing co-monomers in order to reduce the weight of component 2 and to incorporate much of component 2 in molar terms. Come under the unsaturated ethers vinyl ethers come closest to this requirement. Among the halogen-containing vinyl ethers is the Vinyl chloroethyl ether is particularly easily accessible.

Claims (4)

Patent claims: 1. A process for the production of copolymers of acrylonitrile, characterized in that that this monomers with halogen - especially chlorine and / or bromine - containing Vinyl ethers alone or with mixtures thereof copolymerized and the built-in Halogen partially saponified or transesterified or the halogen groups converted to ammonium compounds by reaction with amines. 2. The method according to claim 1, characterized in that that in addition to acrylonitrile and halogen-containing, copolymerizable vinyl ethers further components capable of copolymerization with hydroxyl or basic components Groups are used in the polymerization. 3. Process according to Claims 1 and 2, characterized in that the amount of acrylonitrile is at least 60, preferably 85 to 95% of the monomers used. 4. The method according to claim 1 and 3, characterized in that additional copolymerization components be used, which have a hydrophilizing effect. Considered publications:
U.S. Patent No. 2,595,575;
Krczil, Kurzes Handbuch der Polymerizationstechnik, Vol. II (1941), pp. 173, 174, 232d and 233. © 509 580/137 11.57 (209 511/2 2. 62)