DE1020458B - Process for the manufacture of spinnable acrylonitrile polymerization products - Google Patents

Description

GERMAN

The invention relates to a process for the production of spinnable acrylonitrile polymerization products, in which acrylonitrile is polymerized in the presence of an "inactive,., isolated polymerization product.

It is known to polymerize monomeric acrylonitrile in the presence of previously formed polymers, in order to form synthetic resins which are used in the manufacture of certain rigid commercial objects, such as table tops, Containers, toys, buttons, combs, etc., that can be cut, rolled and machined.

According to the invention it has now been found that the polymerization of acrylonitrile in the presence of Polymers of diamides or amido esters of aliphatic, unsaturated dicarboxylic acids for the Manufacture of fibers or threads, especially textile thread, results in suitable products when the polymerization carried out in the presence of a small amount of another monomeric olefinic compound will.

A particular advantage of the products made in this way is that they are with a Solids content of over 25% can be brought into solution. This results in, for example in the production of textile fibers, substantial savings in solvents and higher spinning speeds. Because these high solids content of the spinning solutions at relatively low temperatures are achieved, there is also no risk of the products discoloring. A formation of gelatinous Particles in the solutions also occurs at temperatures below 100 ° in contrast to the known Acrylonitrile polymerization products do not occur. The products have high tensile strength and high ductility and are easily dyed and in this respect the known polyacrylonitriles used for fiber production think.

In addition to the acrylonitrile, as indicated above, a further monoolefin compound is used in the polymerization in an amount of 15.0 to 0.5 percent by weight, based on the total of the monomeric compounds. These compounds include compounds which contain a - CH == C group or a CH _{2 = C group.} The amount of acrylonitrile is chosen so that the end product contains 60 to 95 percent by weight of acrylonitrile. Products that contain less acrylonitrile are less suitable for fiber production if acrylonitrile is not added to the spinning solutions. This is possible because the products produced according to the process of the invention are compatible with acrylonitrile and also with various other monomers which are otherwise incompatible with polyacrylic compounds.

As already mentioned, the polymerization takes place in the presence of an "inactive" polymerization product,

procedure

for the production of spinnable
Acrylonitrile polymerization products

Applicant:

Eastman Kodak Company,
Rochester, NY (V. St. A.)

Representative: Dr.-Ing. W. Wolff, patent attorney,
Stuttgart-N, Lange Str. 51

Claimed priority:
V. St. v. America October 21, 1952

Harry Wesley Coover Jr.

and John Richard Caldwell,

Kingsport, Tenn. (V. St. A.),

have been named as inventors

that is, a polymerization product which has already been separated from its polymerization mixture is carried out. To prepare these polymerization products, maleic acid amides (R) (R ₁ ) · N · CO · CH: CH · CO-N (R ₁ ) (R), where R and R ₁ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms , e.g. B. Maleic acid amide itself, N-methyl maleic acid amide, N-ethyl maleic acid amide, N-propyl maleic acid amide, N-isopropyl maleic acid amide, Nn-butyl maleic acid amide, N, N '~ dimeth \ dmaleic acid amide, Ν, Ν'-diethyl maleic acid amide, N, N'-di-n- Butyl maleic acid amide, N-methyl-N'-ethyl maleic acid amide, N, N'-tetramethyl maleic acid amide, Ν, Ν'-tetraethyl maleic acid amide, N, N-dimethyl-N ', N'-diethyl maleic acid amide; Fumaric acid amides trans- (R) (R ₁ ) -N-CO-CH: CH-CO-N · (R ₁ ) (R), where R and R _{1 have} the meanings given, e.g. B. fumaric acid amide itself, N-methyl fumaric acid amide, N-ethyl fumaric acid amide, N-propyl fumaric acid amide, N-isopropyl fumaric acid amide, N ~ n-butyl fumaric acid amide, Ν, Ν'-dimethyl fumaric acid amide, N, N'-diethyl fumaric acid amide,-diethyl fumaric acid amide, Butylfumaric acid amide, N-methyl-N'-ethylfumaric acid amide, N-methyl-N'-butylfumaric acid amide, N, N'-tetramethy] fumaric acid amide, Ν, Ν'-tetraethylfumaric acid amide, N, N-dimethyl-Ν ', Ν'-diathaurylfumide ( R) (R ₁ ) · N · CO · C: (CH ₂ ) · CH ₂ -CO-N- (R ₁ ) (R), where R and R _{1 have} the meanings given, e.g. B. Itaconic acid amide itself, N-methyl itaconic acid amide, N-ethyl

709 SOS / 295

3 4

itaconic acid amide, Nn-butyl itaconic acid amide, N, N'-di- can emulsifiers, e.g. B. sodium lauryl sulfate, namethylitaconic acid amide, Ν, Ν'-diethyl itaconic acid amide, trium isobutylnaphthalene sulfonate, sulfonated fatty acid-N, N'-butyl itaconic acid amide, Ν, Ν'-tetramethyl itaconic acid amide, alkali metal salts of alkane sulfonic acid or sulfonated acid; Citraconamide (R) (R ₁ ) -N-CO-C- ether. In order to give the end products a (CH ₃ ): CH · CO · N- (R ₁ ) (R), where R and R _{1 have} the 5 greater solubility, chains turn out to have the meanings given, e.g. B. citraconamide regulators such. B. hexyl, octyl, lauryl, dodecyl itself, N-methyl citraconamide, N-ethyl citracon or myristyl mercaptans, as suitable. To shorten acid amide, Nn-butylcitraconamide, Ν, Ν'-dimethyl- the polymerization time, reducing agents such as citraconamide, Ν, Ν'-diethylcitraconamide, N, N'-alkali bisulfites, can be used. Butylcitraconamide, Ν, Ν'-Tetramethylcitracon- to The isolated preformed homopolymer or acid amide. Copolymer is preferably used in the poly

These specified compounds can be self-merization catalyst-containing aqueous medium

of course also suspended as a further monoolefin compound. The suspension or solution is for example

Heated together with the acrylonitrile as a monomeric starting point for 30 minutes to 24 hours. Afterward

products used in the polymerization. 15 becomes the mixture of the acrylonitrile and the other

_{Acrylamides CH 2} : C (R ₃ ) · monoolefin compound added are also suitable. After adding

CO · N · (R ₁ ) (R), where around R ₁ the total mixture specified above again

Have meanings and R _{3 is} a hydrogen atom or conditions held until the acrylonitrile and the other

means a methyl group, e.g. B. Acrylic acid amide itself, added monoolefin compound essentially poly-

N-Methylacrylsäureamid, N-Äthylacrylsäureamid, N-Iso- ao are merized. Alternatively, the inactive Horno-

propyl acrylic acid amide, N-n-butyl acrylic acid amide, meth- polymer or mixed polymer of an aqueous one

Acrylic acid amide, N-methyl methacrylic acid amide, N-ethyl mixture, solution or emulsion, which consists of the mixture

methacrylic acid amide, N-isopropyl methacrylic acid amide, the acrylonitrile, the other monoolefin compound and

Ν, Ν-dimethylacrylic acid amide, Ν, Ν-diethylacrylic acid containing the polymerization catalyst, added

amide, Ν, Ν-dimethyl-niethacrylsäureamid, Äthacryl- 25 be. Also the acrylonitrile and the other

acid amide, N-methyl-ethacrylic acid amide, a-propyl acrylic monoolefin compound and the inactive polymerization

acid amide, N-methyl-a-butyl acrylic acid amide; Amido product are mixed together. The mix will

maleic acid ester cis- (R) (R ₁ ) -N-CO-CH: CH-CO-O R ₂ , then one containing the polymerization catalyst

where R and R _{1 have} the abovementioned meanings added to aqueous medium. The following examples

and R _{2 is} an alkyl group having 1 to 4 carbon atoms 30 serve to further explain the process according to FIG

is e.g. B. Amidomalemsäuremethylester, -äthylester, -pro- of the invention,

pylester, -n-butylester, methyl-, ethyl-, butylamido- Example 1 maleic acid methyl ester, methylamido butyl maleic acid

ester, dimethylamidomaleic acid methyl ester, -ethyl- 2 g of polyfumaric acid amide in 100 ecm of water,

ester, dimethylamidomaleic acid n-butyl ester, dibutyl 35 0.1 g ammonium persulfate, 0.1 g potassium disulfite,

amidomalemic acid methyl ester; Amidofumaric acid ester containing 7.8 g of acrylonitrile and 0.2 g of vinyl acetate, dissolved.

trans- (R) (R ₁ ) - N • CO • CH: CH • CO • OR ₂ , e.g. As the Man, the solution is stirred for 16 hours at 25 ⁰ C polymerize

esters given under the amidomaleic acid esters; and the resulting polymerization product is filtered off. Amidoitaconic acid ester (R ₁ ) (R) N CO CH ₂ C: (CH ₂ )

CO-OR ₂ OdCr (R ₁ ) (R) N-CO-C: (CH ₂ ) -CH ₂ -CO-OR ₅ Amidocitraconic acid ester (R ₁ ) (R) N CO CH: C (CH ₃ )

After drying, the product has a weight of 40.9.7 g and, as an analysis shows, has a content of 19 percent by weight of fumaric acid amide.

CO-OR ₂ or (R ₁ ) (R) N-CO-C (CH ₃ ): CH-CO-OR ₂ ;

Acrylic acid ester CH ₂ : C (R ₃ ) • CO • OR ₂ ; Vinyl carbon example ~

acid ester CH ₂ : CH · C · CO · R ₄ , where R _{4 is} 1 to 3 g of a copolymer of acrylonitrile

Represents an alkyl group having 3 carbon atoms. 45 and maleic acid amide, which contains 76 weight percent maleic

For the production of the acid amide contained in the polymerization, dissolved in 100 ecm of water, which with

The inactive polymerization product used can be 0.1 g ammonium persulfate and 0.1 g potassium disulfite

the same connection as it is offset as another mono-olefin. The solution is for 18 hours at 3O ⁰ C to

compound is used, rolled during the polymerization and then with 6.4 g of acrylonitrile and 0.6 g

be used. Depending on the required self-50 maleic acid amide added. One continues the polymerization

However, it turns out to be shedding the end product in 48 hours at 35 ^: C. The resulting polymerization

In many cases, when appropriate, various compounds are precipitated and centrifuged. After drying

to use, so that the end product from three is obtained 9.5 g of a polymerization product, the

consists of different components. Contains 64 percent by weight of acrylonitrile.

Further suitable monoolefin compounds are at 55.

for example styrene, a-methylstyrene, p-acetaminostyrene, egg spie

α-Acetoxystyrene, vinyl chloride, vinylidene chloride, ethyl 1.0 g of polymethylfumaric acid amide is dissolved in 60 ecm of water

vinyl ether, isopropyl vinyl ether, isopropenil methyl ketone, introduced, the 1 ecm of the sodium salt of 7-ethyl

Contains ethyl isopropenyl ketone, methyl vinyl ketone, ethyl vinyl 2-methylundecane-4-sulfonic acid (Tergitol No. 4),

ketone, dimethyl maleate, Maleinsäurediäthylester, 60 The mixture is agitated intensively for 1 hour at 50 ⁰ C.

Fumaric acid diisopropyl ester, acrylic acid, methacrylic acid, and after cooling with 7.8 g of acrylonitrile, 1.2 g of amido

Fumaronitrile, methacrylonitrile, N-vinylphthalimide, vinyl fumaric acid methyl ester, 0.1 g ammonium persulfate and

butyrate, vinyl sulfonamide, ethylene and isobutylene. 0.1 g of sodium disulfite are added. The mixture is left

The polymerization is preferably carried out in an aqueous medium and polymerize at 25 ° C. for 16 hours with circulation. There are, however, 65 is thus obtained in 92 ° / ₀ yield a Polymerisationsproorganische solvents or solvent mixtures, domestic product containing 77 percent by weight of acrylonitrile, such as aqueous acetone, is suitable. To speed up the. Polymerization are suitable for. B. organic peroxides, example

Perborates, ketazines and azines. The reaction temperature 3 g of a copolymer of Ν, Ν'-dimethylamido-

is expediently between 25 and 75 ° C. Furthermore, 70 fumaric acid amide and methacrylic acid methyl ester, the

5 6

28 weight percent of the diamide containing are precipitated in product by adding acetone and through

100 ecm of water, the 3 ecm of a sulfonated ether separated by centrifugation.

(Triton 720), emulsified. Adds to this emulsion.

one 6.5 g of acrylonitrile, 0.5 g of Ν, Ν'-dimethylfumaric acid - Example 10

amide, 0.15 g potassium persulfate and 0.1 g sodium disulfite. 5 1 g of poly-N-isopropyl acrylic acid amide in 60 ecm

The emulsion is heated for 12 hours to 35 ⁰ C and then introduced water containing 1 cc of the sodium salt of

cooled to room temperature. The polymerization 7-ethyl-2-methylundecane-4-sulfonic acid (Tergitol No. 4)

product is precipitated, filtered off, washed and dried. contains. The mixture is ^{reacted at 50 °} C. for 1 hour,

As an analysis shows, it contains 65.1 percent by weight, cooled and mixed with 8 g of acrylonitrile, 0.5 g of N-isopropyl

Acrylonitrile. i ° acrylic acid amide, 0.1 g ammonium persulfate and 0.1 g

Example 5 Sodium bisulfite added. Polymerizing for 10 hours

at 25 ° C with agitation of the mixture yields in 85%

There are 2 g of poly-N, N'-diisopropyl maleic acid amide yield a polymerization product which, like a

in 80 ecm of water, which shows 3 g of the sodium salt of the 7-ethyl analysis, contains 79.5 percent by weight of acrylonitrile. Contains 2-methylundecane-4-sulfonic acid (Tergitol No. 4), 15

emulsified and the emulsion with 7 g of acrylonitrile, 1 g of Iso- example 11

propenyl acetate, 0.1 g potassium persulfate and. 0.1 g of sodium 3 g of a copolymer of N, N-Di-

disulfite added and 16 hours with circulation on methylacrylic acid amide and vinyl acetate, the 60 weight-

Heated to 35 ° C. The emulsion is then to room percent Ν, Ν-Dimethylacrylsäureamid contains, in 50 ecm

cooled temperature and the precipitated polymerization 20 a 50% solution of acetonitrile dissolved in water,

the product is filtered off, washed with distilled water. The solution is mixed with 5.4 g of acrylonitrile, 0.4 g of N-methyl

and dried. The product contains 21 percent by weight methacrylic acid amide, 0.1 g ammonium persulfate and 0.1 g

Maleic acid amide. Sodium bisulfite added and 16 hours at 40 ⁰ C poly-

Example 6 merized. The polymerization product can be in 92%

25 yield to be precipitated. It contains how an analysis

3 g of isopropyl poly-dimethylamidocitraconate shows 54 percent by weight of acrylonitrile.

are dispersed in 100ccm water. .

salt of 7-ethyl-2-methylundecane-4-sulfonic acid, 0.1 g of Example IZ

Ammonium persulfate, 0.1 g sodium disulfite, 6.9 g acrylic 2 g of a copolymer of N-methyl

nitrile and 0.1 g of N-methyl methacrylic acid amide. 30 acrylic acid amide and acrylic acid amide, the 30 weight

The solution is maintained for 16 hours at 30 ⁰ C and then N-percent Methylacrylsäureamid contains, in 70 cc

cooled to room temperature. The polymerization water introduced, the 0.1 g of sodium bisulfite, 0.1 g

product is precipitated, filtered off, treated with distilled ammonium persulfate, 8.1 g acrylonitrile and 0.9 g amido

Water washed and dried. It contains how a maleic acid contains methyl ester. The solution is left

Analysis shows 68.5 weight percent acrylonitrile. 35 polymerize for 16 hours at 35 ° C, the poly-

. - ₁₇ merization product and dries it. The yield

Example 7 _to p _o iy _me risationsprodukt is 90%. The product

6 g of a copolymer of isopropylamidomalein contains, as an analysis shows, 81 percent by weight of acrylic

acid methyl ester and methylamidocitraconic acid isopropyl nitrile. . .

pylester, which contains 70% of the maleic acid ester, are 40 examples

emulsified in 100 ecm of water, the 4 ecm of the sodium 2 g of poly-N, N'-dimethylitaconic acid diamide salt of 7-ethyl-2-methylundecane-4-sulfonic acid (Ter- emulsified in 80 ecm of water, the 3 ecm of sodium salt which contains gitol No. 4). The emulsion is containing 3.5 g of acrylic 7-ethyl-2-methylundecane-4-sulfonic acid (Tergitol No. 4) nitrile, 0.5 g of vinyl chloride, 0.1 g of sodium disulfite and 0.1 g. The emulsion is mixed with 7.2 g acrylonitrile, 0.8 g of potassium persulfate and 45 for 8 hours under agitation vinyl acetate, kept O ₁ Ig of potassium persulfate and 0.1g Natriumauf 35 ° C. After the emulsion has cooled to bisulfite and stirred for 16 hours at room temperature, the precipitated polymerization is kept at 35.degree. Thereafter, the emulsion is filtered off on room product, washed with distilled water, cooled to temperature, the precipitated polymerization and dried. The polymerization product, filtered off and washed with distilled water, as an analysis shows, contains 35% acrylonitrile. 50 and dried. The product contains 21 percent by weight

_. . , "Ν, Ν-dimethylitaconic acid diamide. The yield is

Example 8 ₉₂₀ /

There are 2 g of poly-N-methylacrylic acid amidine 100 cc of Example 14

Dissolved water, 0.1 g of ammonium persulfate, 0.1 g of 3 g of a copolymer of acrylic acid

Potassium bisulfite, 7.5 g of acrylonitrile and 0.5 g of N-methyl-55 amide and methacrylic acid ester, which is 80 percent by weight

contains acrylic acid amide. The solution is allowed to contain acrylic acid amide for 16 hours, dissolved in 100 ecm of water

polymerize at 30 ^° C. and filter the 0.1 g of potassium persulfate, 0.1 g of sodium bisulfite, 6.5 g of acrylic

Polymerization product from. The product weighs according to the nitrile and 0.5 g of acrylic acid amide it contains. The solution

Drying 8.7 g. An analysis shows that it contains is kept at 35 ° C for 16 hours and then on

74.5% acrylonitrile. 60 room temperature cooled. The precipitated poly-

Beisniel 9 merization product is filtered off with distilled

Water washed and finally dried. the

3 g of a copolymer of acrylonitrile and the yield is 95%. The product contains, like a

N-methyl methacrylic acid amide showing 76 weight percent analysis, 65 weight percent acrylonitrile.

Contains N-methyl methacrylic acid amide in 100 ecm 65.

Water together with 0.1 g of ammonium persulfate and example

0.1 g potassium bisulfite dissolved. The solution is 3 g of poly-N-methyl-methacrylic acid amide in 100 ecm for 18 hours

circulated at 25 ⁰ C and then with 6.1 g of acrylonitrile and water are dissolved and 0.1 g of ammonium persulfate,

0.5 g of N-methyl methacrylic acid amide are added and the 0.1 g of sodium bisulfite, 6.9 g of acrylonitrile and 0.1 g of maleic

Polymerization continued for 48 hours at 25 ° C. The 70 acid dimethyl ester was added. The solution will take 16 hours

the kept at 30 ⁰ C and then cooled to room temperature. The precipitated polymerization product is filtered off, washed with distilled water and dried. As an analysis shows, the product contains 68.9 percent by weight of acrylonitrile.

example

1 g of polycitraconic acid amide is introduced into 60 ecm of water which contains 1 ecm of the sodium salt of 7-ethyl-2-methylundecane-2-sulfonic acid (Tergitol No. 4). The mixture is agitated for 1 hour at 5O ⁰ C. The emulsion is then cooled and 8.4 g of acrylonitrile, 0.1 g of methyl methacrylate, 0.1 g of ammonium persulfate and 0.1 g of sodium bisulfite are added. The mixture is allowed to polymerize for 16 hours at 35.degree. C. and a polymerization product is obtained in this way in 96% yield which, as analysis shows, contains 84 percent by weight of acrylonitrile.

The physical properties of the products made according to the process are from the following The list can be seen. In each case, the product indicated in the examples was used in the specified solvent dissolved. The solution was spun in a precipitation bath.

Lineup

example

solvent

tensile strenght

g / denier

Elasticity

Bonding temperature

Shrinkage in

boiling water

9
10
11
12th
13th
14th
15th
16

Dimethylformamide Dimethylformamide Dimethylacetamide Dimethylacetamide Dimethylacetamide Dimethylacetamide Dimethylformamide Dimethylformamide Dimethylformamide Dimethylformamide, Dimethylacetamide, Dimethylformamide, Dimethylformamide Dimethylacetamide Dimethylacetamide Dimethylformamide Dimethylacetamide

3.2 23 215 3.3 26th 205 3.8 33 210 3.7 32 215 195 3.8 37 220 3.7 24 210 3.3 26th 215 3.2 26th 200 3.4 35 198 3.9 28 205 3.1 27 185 28 200 3.8 26th 205 26th 205 3.7 22nd 200 3.6 21 210

9 7 6

9 7 8

10 7 7

12 In addition to the solvents specified, ethylene carbonate, ethylene carbamate, γ - butyrolactone, N-methyl-2-pyrrolidone, Ν, Ν-dimethylcyanamide, N ₁ N-dimethylcyanacetamide, N, N-dimethyl- / 5-cyanopropionamide, glycolonitrile (formaldehyde cyanohydrin) are suitable , Malonitrile, ethylene cyanohydrin, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, tetramethylene sulfoxide, N-formylpyrrolidine, N-formylmorpholine, N.N'-tetramethylene methanephosphonamide. However, Ν, Ν-dimethylformamide and N ₁ N-dimethylacetamide proved to be particularly suitable. In the preferred solvents, the products can / be brought into solution ₀ ° with a solids content of 25 to 40 wt. In addition to the production of threads, the products are suitable for the production of films, foils, panels, plates, blank films for photographic materials or the like. The acrylonitrile content of the products should generally be above 60%. If this is not the case, an appropriate amount of polyacrylonitrile can be added to the spinning solution.

so these physical mixtures are stable.

Claims (8)

Patent claims: 1. A process for the preparation of spinnable acrylonitrile polymerization products, in which a Dispersion of monoinerem acrylonitrile in the presence of an "inactive .., i.e. a polymerization product, which has been separated from its polymerization mixture, which consists of a diamide or a Amidoesters of aliphatic α, / 3-unsaturated dicarboxylic acids or consists of an acrylamide or acrylic ester or contains such a compound, is polymerized, characterized in that during the polymerization as monomeric compounds 85.0 to 99.5 percent by weight of acrylonitrile and 15.0 to 0.5 percent by weight of a further monoolefin compound can be used and that the inactive polymerization product is used in such an amount it is that the final product contains at least 60 weight percent acrylonitrile. 2. The method according to claim 1, characterized in that for the preparation of the inactive polymerization product or an acrylic acid amide CH ₂ : C (R ₃ ) -CO-N- (R) (R ₁ ), a maleic acid amide cis- (Rj) as a further monoolefin compound (R) -N- CO • CH: CH • CO • N (R) (R ₁ ), a fumaric acid amide trans- (R ₁ ) (R) -N-CO-CHiCH-CO-N- (R) (R ₁ ), an itaconic acid amide (R ₁ ) (R) N - CO C: (CH.,) - CH, CO N (R) (R ₁ ), citraconic acid amide (R ₁ ) (R) -N- CO-C- (CH ₃ ): CH · CO · N (R) (R ₁ ) can be used, where R and R _{1 are} each a hydrogen or an alkyl group _{having 1 to 4 carbon atoms and R 3 is} a hydrogen atom or a methyl group . 3. The method according to claims 1 and 2, characterized in that an amidomaleic acid ester OR ₂ · CO · CH: CH · CO · N (R) (R ₁ ), an amidofumaric acid ester trans-fR,) (R) · N CO CH: CH CO OR ₀ , an amidoitaconic acid ester OR ₀ CO C: (CH,) CH ₀ -CO-N- (R) (R ₁ ) *) Physical mixture of 95 parts of the product and parts of polyacrylonitrile. ** ') Physical mixture of 50 parts of the product and parts of a polyacrylonitrile. the 95% acrylonitrile and 5% Contains vinyl acetate. ' or (RJ (R) · N · CO - C: (CH ₂ ) · CH ₂ · CO · OR ₂ , an amidocitraconic acid ester OR ₀ · CO · C (CH ₃ ): CH · CO-N- (R) (R ₁ ) or (R ₁ ) (R) "- N-CO-C- (CH ₃ ): CH-CO-OR ₂ or an acrylic acid ester CH ₂ : C (R ₃ ) · CO-OR ₂ or a vinyl carboxylic _{acid ester CH 2} : CH · C-CO-R ₄ is used, where R and R _{1 are} each a hydrogen or an alkyl group _{having 1 to 4 carbon atoms, R 2 is} an alkyl group having 1 to 4 carbon atoms, R _{3 is} hydrogen or a methyl group and R _{4 is} an alkyl group having 1 to 3 carbon atoms. 4. Process according to Claims 1 to 3, characterized in that in the presence of a peroxide polymerization catalyst a dispersion of acrylonitrile, N-isopropyl acrylamide and one isolated poly-N-isopropyl acrylamide is heated, until the monomeric compounds are substantially polymerized. 5. Process according to Claims 1 to 3, characterized in that in the presence of a peroxide polymerization catalyst Acrylonitrile, vinyl acetate and polyfumaramide are heated until the monomers Compounds are essentially polymerized. 6. Process according to Claims 1 to 3, characterized in that in the presence of a peroxide polymerization catalyst Acrylonitrile, vinyl acetate and poly-N, N'-dimethylitaconic acid amide is heated, until the monomeric compounds are substantially polymerized. 7. Process according to Claims 1 to 3, characterized in that in the presence of a polymerization catalyst a dispersion of acrylonitrile, methacrylic acid methyl ester and polycitraconic acid amide is heated until the monomeric compounds are substantially polymerized. 8. Process according to Claims 1 to 3, characterized in that in the presence of a peroxide polymerization catalyst a dispersion of acrylonitrile, N-methyl methacrylic acid amide and a isolated copolymer of N-methyl methacrylic acid amide and heating acrylonitrile until the monomeric compounds substantially polymerize are. Considered publications:
German patent specification No. 818 693. © 709 808/295 11:57