DEF0010278MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: October 30, 1952. Advertised on November 17, 1955

GERMAN PATENT OFFICE

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

It has now been found that halogen-containing, especially chlorine- and / or bromine-containing, not copolymerizable Alcohols which are themselves etherified with alcohols capable of copolymerization, polymerize particularly easily with acrylonitrile uhd to form valuable products with remarkably good solubility to lead. As chlorine-containing, non-copolymerizable alcohol components come in Question z. B. ethylene chlorohydrin, i-oxy-3-chloropropane, 1,2- Dioxy - 3 - chloropropane, 1 - Oxy - 3 - chloropropane, i-oxy-3-bromopropane. As copolymerizable alcohol components come into question z. B. vinyl alcohol, Allyl alcohol, methallyl alcohol, crotyl alcohol, chlorallyl alcohol. The chlorine-containing Copolymers 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 the aqueous or organic phase and with all usually amines used for aminations. It can also be used for dyeing under certain conditions the chlorine will be partially hydrolyzed. the

509 580/137

F 10278 IYbI39c

Halogen-containing ethers can also be used together with advantage With basic esters, ethers, sulfones or hydrocarbons containing amino groups or Amides, with basic groups expediently in salt form which are capable of copolymerization Group contain, are copolymerized with acrylonitrile. Next is the interpolymerization with compounds, which increase the hydrophilicity of the polyacrylonitrile are advantageous.

ίο As additional comonomers that are hydrophilic acting, 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 6ο ⁰ / ,, be at least of the monomers used. However, it is preferred to work in such a way that the amount of acrylonitrile used 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 that spread through better coloring properties than the previously known products are processed.

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. Activation will made by peroxidic compounds alone or with the addition of reducing substances.

It is known for copolymers of acrylonitrile with vinyl chloroacetate or allyl chloroacetate after treatment with ammonia or amines to obtain products with improved colorability. However, there are limits to the choice of amines and the amination conditions, since the ester group saponified relatively easily and thus the dye-affine group is split off. Above all, it has to be showed that the intercession aminated on such Copolymers are not washable. Obviously, under the washing conditions, the substituted one becomes Aminoacetic acid residue is split off. The one here claim th copolymers allow amination under a wide variety of conditions and result in completely washfast colorations.

ICs are also known to amine copolymers of acrylonitrile and chloro-oxy-propyl allyl ether. A reworking has shown that this copolymer with dimethylformamide does not produce any spinnable material Can produce 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 added:

90 g acrylonitrile,
iog vinyl chloroethyl ether,

ι cc hydrogen peroxide (35 ° / _o solution).
The polymerization is initiated by the dropwise addition of sodium formaldehyde sulfoxylate solution and brought to the end. A finely powdered copolymer results. Yield 81 g.

The product extracted with methanol has 3.52 and 3.43 ⁰ I ₀ Cl. It corresponds to a vinyl chloroethyl ether content 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 ^{treated with a 5% aqueous solution of cyclohexylamine at 98 0} for ^{1 1} ₂ hours in a liquor ratio of 1:50, then washed with hot water, then at 80 ° with 2% acetic acid or i% 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. Alizarin pure blue FFB, for example, which is dyed at the boil in excess in the presence of 4% formic acid I ¹ Z for ₂ hours, absorbs 12 ⁰ Z ₀ (calculated on the fiber material). 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 SP and a perfect black with azo acid black 3 B1. Also for other classes of dyes, the dye affinity of the fiber according to the invention is significantly improved compared with 100 ° / ₀ existing polyacrylonitrile material. For example, with nouns dyes such as Sirius red 4 B 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: ι 500 g water,

5 g sodium paraffin sulfonic acid,
30 g table salt, 5 g magnesium sulfate · 7 H 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 ° / _o solution),
ι g glacial acetic acid,

40 g of monomer mixture.

The polymerization is allowed to start with 40 ecm of a dilute sodium formaldehyde sulfoxylate solution (7 g sodium formaldehyde sulfoxylate in 1000 g water) and the following three solutions are then added to the reaction vessel in a volume ratio of 1: 1: 1 over the course of 2 hours: First, sodium formaldehyde sulfoxylate, 7 g in 1000 g H ₂ O, second monomer mixture, 760 g, third solution of 7 g of hydrogen peroxide 35 ° / _o ig ecm in 1000 fleet.

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.

580/137

F 10278 IYbI39c

The result is a copolymer with 2.93% chlorine; this corresponds to around 9% vinyl chloroethyl ether. r \ _r (i ° / _o solution in dimethylformamide): 4.6.

20 weight parts of this interpolymer are dissolved in 80 parts by weight of dimethylformamide containing 2% _ morpholine and heated for 2 hours at 95 ^0th The solution obtained is spun in a known manner. The fibers are washed, dried and hot ^{drawn 6 x} / ₂ times. They have a strength of 3.1 g / den. The fibers can be dyed with acidic dyes such as alizarin pure blue FFB, azo acid black 3 Bl, anthralan red G, light green SP and cellitone dyes.

Example 3

The procedure is as described in Example 2, but the following monomer mixture is used:
700 g acrylonitrile,
50 g chloroethyl vinyl ether,
50 g of allyl ethyl carbonate.

The result is a copolymer containing 1.53% Cl (around 5% vinyl chloroethyl ether). η _τ (i% in dimethylformamide): 3.88.

Example 4

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% chlorine; this corresponds to a content of allyl chloroethyl ether of 7%. The polymer yield is lower than in Example 2.

On the basis of numerous experiments it has been found that among the ethers of vinyl alcohols, allyl alcohol, Methallyl alcohol works best with the ethers of vinyl alcohols in interpolymerization with acrylonitrile, on the other hand the ethers of crotyl alcohol polymerize into the real poor.

Furthermore, calibration has shown that with increasing installation of the second component, the fiber properties especially the softening point of the fibers of the fibers produced from the copolymers deteriorate.

Conversely, with increasing incorporation of the halogen-containing ether, the colorability after amine aftertreatment increases improved.

In the interests of fiber properties and the ability to be dyed, it is therefore desirable to use as much as possible to use small halogen-containing co-monomers in order to have little of component 2 in terms of weight and in terms of molar to incorporate a lot of component 2. This requirement comes among the unsaturated ethers the vinyl ethers closest. Vinyl chloroethyl ether is one of the halogen-containing vinyl ethers 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 optionally the built-in Halogen partially saponified or transesterified or the halogen groups are closed by reaction with amines Converts ammonium compounds. 2. The method according to claim 1, characterized in that that in addition to acrylonitrile and halogen-containing, copolymerizable vinyl ethers still further components capable of copolymerization with hydroxyl or basic groups polymerization can be used. 3. Process according to Claims 1 and 2, characterized in that the amount of acrylonitrile is at least 60, preferably 85 to 95 ° / ₀ , 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.