DE1050055B - Process for modifying high molecular weight organic substances containing nitrile groups using an inorganic nitrogen base - Google Patents

Description

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EXPLAINING PAPER 1050 055

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REGISTRATION DATE: SEPTEMBER 24, 1955

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EDITORIAL: FEBRUARY 5 A R 1 959

The invention relates to the preparation of high molecular weight compounds with amidoxime groups. Low molecular weight amidoximes according to the formula

, N-OH
R - C *

NH ₂

were by Lossen (Ann., 166 [1873], p. 295), but especially by Tiemann and P. Kruger (Ben, 17 [1884], P. 1685).

A systematic study of the amidoximes has only rarely been carried out. By Buu-Hoi and Cagniant (Grignard, Traite de Chimie Organique, T XV, p. 710) - probably as a result of experimental difficulties - the attention is particularly drawn to the aromatic ranks have been directed.

According to a more recent publication (S. Soloway et al, Anal. Chem., 24 [1952], p. 898) the reaction of the HydroKylamins on non-polymeric nitriles for colonial Determination of nitriles applied.

Although lower molecular weight amidoximes and their reaction products have been investigated, polymers are with amidoxime groups has not yet been described.

As is known, it has been proposed to use polyacrylic fibers in the presence of hydroxylamines ^ and cupric salts to color. The same proposal can also be seen that the hydroxylamine or its derivatives can only be used as a reducing agent for the cupric salts (US Pat. No. 2,653,074).

From USA. Patenlschrift-2671066 the viscosity of the Polyacrylnitrillösungen is further known by intimately mixing the polymer with the suitable organic solvent and a minor amount, ie 0.1 to 5 ° / ₀ of certain of hydrochlorides of organic amines, for example. B. also hydroxylamine chlorohydrate to reduce. As stated in this patent specification, this influence on viscosity is in all probability only due to purely physical factors.

The invention creates the possibility of producing high molecular weight substances with amidoxime groups. Because the amidoxime groups tend to form rings, this term also includes those from the same Reaction as a result of the mutual interaction of the amidoxime group-derived reaction products.

The invention is based on the formation of high molecular weight substances containing amidoxime groups in the at least partial reaction of hydroxylamine with the nitrile groups of high molecular weight organic nitrile groups Fabrics.

Other methods of making lower molecular weight amidoximes, e.g. B. by reaction of Modification method

of nitrile groups

high molecular weight organic substances

by an inorganic nitrogen base

Applicant:

Gevaert Photo-Products NV,
Mortsel, Antwerp (Belgium)

Representative: Dr. W. Müller-Bore, patent attorney,
Braunschweig, Am Bürgerpark 8

Claimed priority:
Great Britain September 24, 1954

Ferdinand Leonard Schouteden,

Wilrijk, Antwerp (Belgium),

has been named as the inventor

Imino ethers, amides and thioamides with hydroxylamine or by the action of NH ,, on chlorinated aldoximes

or by reducing oxyamidoximes or nitroso acids are known. Whether these reactions too are applicable to macromolecular substances has not been investigated; In any case, they cannot go with the Compare method according to the invention because the with

Polymers corresponding to the low molecular weight starting materials are difficult to obtain.

The main reaction for the production of high molecular weight substances with amidoxime groups according to the invention can be illustrated by the following general formula

become light:

M - (CN) _B

45

y-NH ₂ OH

M -

N-OH

NH,

In this formula, M is the macromolecular skeleton into which functional groups of various types may have been introduced; χ a certain number of nitrile groups in the high molecular weight starting material; y ' a certain number of amidoxime groups in the reaction product.

The reaction can be carried out until all of the nitrile groups react with hydroxylamine have, or they can be at any earlier stage

809 748/462

to be interrupted. The reaction can take place all at once. In this way, the products of the process can be used or in stages. In addition, other reactions can improve the properties of solutions of the functions of one or more different polymoleculars present as starting materials in the macro Use the functional groups present in the substance. In combination with other films go hand in hand. 5 forming polymers they are capable of the properties

Typical examples of reactions which advantageously influence the formation of oxime with the amide of the films cast therefrom go together, are z. B. hydrolysis, influences.

or intramolecular ring formation, neutralizing of the modified high molecular weight substances can also

Acid groups and elimination of HCl in chlorine-containing ones for the production of film bases and / or exterior copolymers. When the macromolecular residue io and inner layers in graphic or photographic

Q X group materials, as raw material for the production of

packaging materials and as a top layer on substrates,

'z. B. as paint, varnish, varnish or adhesive layer

Films, foils, fibers "SrfiJ other objects

contains, in which X —NH ₂ , —NHR, —NRR ', Halo- 15 serve. The high genatom containing amidoxime groups or a complement for the formation of anhydride molecules can be used in the production of groups, HONH ₂ can react with these groups under paper either as an additive to the paper pulp or also to form hydroxamic acid. Impregnating agent used for the finished paper web

The order and degree of these will be different. The invention also includes chemical Reactions can be controlled in any way. 20 Reaction of already deformed CN-containing Hoch-Zur Implementation of the molecular method according to the invention with hydroxylamine.

All nitrile group-containing substances are used as the starting materials. The modified high-molecular substances are used

high molecular weight substances into consideration: continue to be used as textile auxiliaries to improve the

<ο,, “. ,,,. T>,,, Properties of known fibers. A very important one

1. Polymers and copolymers, including ßlockpoly-. ,,. ,,. ,. , "» ..,. ,1 ·. j τ _Γ

^J , ,, j ^J,. . , v,., .-; he area of application is the possibility of adding, using polymerizable nitriles, ^ö , ° τ ·· ν χ * · ν jj \,, „, τ ,,,. ofj improvement of the properties, especially of the attached graft polymer, possibly with bridges, .., ° .. ^ _XT u ü · tt
between the main chains · coloring capacity of fibers containing CN groups.
_o . j ...,. , j ', ..,, 111 If you add them to other colloidal solutions,

2. any natural or synthetic macromolecular,,,,. , _r . , ,, «,,, _u L λ, j ..., ·. ·. .... 1 ·, j, 1 ·. their theological properties are conspicuously be-substance that is cyanathylated with acrylonitrile and / or with ■ _a ο * τ \ · · χ -u · j tt a «ν j. ν

, · · U χτ · i. -tta ■ ί 3 ° influences. This is important in the production of photographic

a polymerizable nitrile is grafted; ° , _{Λ / Γ,.} . "", °. · Ι -Λ

r, π, ι. t> ii j? jii. This material is of great importance because it occurs frequently

3. Polymers or polycondensation products, their .... ....., _, °. ,, - °,.

r · u IJAVJ-J -χ -i. -i ui viscosity and solidification point of the emulsions

In addition, carboxyl or anhydride _{groups are held in} groups.

term hydroxy compounds are esterified. greases and / or binders in photosensitive

Particularly suitable polymers are, for. B. use those of the 35 emulsions.

Acrylonitrile · ?, methacrylonitrile and vinylidenecyanide alone due to their property, different chemical or to bind and fix in combination with other polymerizable substances, the substances, and macromolecular substances, e.g. B. Polyvinyl driving products particularly advantageous in materials alcohol, polyvinylamine, polyacrylamide or methacrylamide, the nature of which is by diffusion chemical cellulose, Alginic acid, starch, zein, gelatin, casein or mixed substances, in particular colors and dyes Derivatives that are cyanäthj liert and / or grafted. educator, is impaired. You can also benefit

The hydroxylamine can be used as a free base or in the form of a smoke filter in cigarettes.

its various known salts can be used. Under certain circumstances there is the fixation of others

In the latter case, the hydroxylamine from the salts must be chemically reversible so that they can be used as ion exchange

gradually or all at once, at least partly in resin, preferably in the form of grains or fibers,

Reaction medium can be released, if it cannot be used,

other way, e.g. B. by hydrolysis, free hydroxyl. -I ₁

amine is formed. Example 1, which forms _{NH 2} OH, can also be used

Substances, e.g. B. ammonium hypochlorite and sodium nitrite, a solution of 50 g polyacrylonitrile in 500 cm ³

be released. The reaction with the high molecular weight dimethylformamide results in 105 g of NH _{2 in succession}

lar starting product can be added in the form of a solution, a —OH-HCl and 75 g of anhydrous Na ₂ CO ₃ .

Dispersion or take place in the swollen state. The mixture is heated to 75 ° C for 3 to 4 hours.

The simplest method for commercial use Then the reaction mixture is sucked off warm and

The process product consists in the use of the precipitated in methanol. After repeated

Reaction mixture immediately after filtering off 55 washing of the precipitate with methanol is the

of the salts formed. If necessary, the nitrated solvent can be removed by centrifugation. then

The reaction product separated by a nonsolvent is dried in vacuo. You get 65 g

and again in a suitable solvent dissolved dry product at 25.5 ° / ₀ N content. Although the

will. Nitrogen content does not match that of polyacrylonitrile

Linear polymers containing amidoxime groups, e.g. B. 60 matches, in which all nitrile groups in amide

modified polyacrylonitrile, the CN groups, oxime groups practical (32.5 ° / ₀ nitrogen) are reacted, are

table are fully implemented, are mostly non-typical properties of amidoximes im

soluble in pure water, but can be detected in acid or reaction mixture; it is insoluble in water,

Alkali-containing aqueous solutions with one but soluble in acidic or basic aqueous solutions.

PH value above or below 7. Apparently it is 65. The HCl solution gives a dark red color _{with FeCl 3,}

This solubility is due to the formation of water-soluble salts. In the infrared spectrum there are practically no C N bands

ascribe. These solutions can be applied to films and more, but probably characteristic bands for the

Shedding or spinning fibers. They get along with the C = NOH group. The fairly low nitrogen

with other solutions, e.g. B. with aqueous solutions on the one hand and the absence of CN bands

of gelatin, polyvinyl alcohol and polyvinyl pyrrolidone. 70, on the other hand, suggests that amidoxime formation (with

Side phenomenon (with

Nitrogen increase) with a
Nitrogen loss).

Example 2

15 g of polyacrylonitrile produced by emulsion polymerization ([η] = 2.9) are dissolved in 300 cm ^{3 of} dimethylformamide. _{Varying amounts of NH 2} OH.HCl (Table I, 2nd column) and the corresponding amounts of Na ₂ CO ₃ , which are just _{sufficient to neutralize the hydrochloric acid present in the NH 2} OH, are added to different amounts of this stock solution. The numbers in the second column show the percentage ratio of the amount of hydroxylamine liberated from the salt (a) to the amount (b) which is required to convert all nitrile groups into amidoxime groups, assuming that to form an amidoxime group each nitrile group with a Hydroxylamine molecule reacts. ^{The mixtures are heated to 75 °} C. for 3 hours in the same way. The reaction mixtures are then filtered off with suction, precipitated in methanol, and the precipitates are washed in fresh methanol and dried.

Table I.

Properties of the reaction products of polyacrylonitrile with various amounts of hydroxylamine

attempt relationship Dimethyl Solubility in n / l O-NaOH No. from 100 formamide n / 10 HCl a 0 + (Empty attempt) - b 20th swells - - C. 40 swells swells - d 60 swells swells + e 80 swells swells 4- f 100 swells + + G 150 swells +

- = insoluble +

soluble

The nitrogen content of the various samples is between 23 and 25%. It should be noted that while of all experiments carried out at room temperature, the polymer remains in solution while the precipitates and the dried reaction products only swell in dimethylformamide.

Example 3

1 g of polyacrylonitrile is ^{dispersed in 100 cm 3 of} butanol, which in turn contains 2.1 g of NH ₂ OH-HCl and 1.5 g of potassium hydroxide. The mixture is heated to 90 ° C. for 3 hours with stirring. The solid particles are filtered, washed first with water and then repeatedly with methanol and dried in vacuo. The modified polymer is insoluble in dimethylformamide, n / 10-HCl and n / 10-NaOH. The particles swell only in n / 10-HCl and, with FeCl _{3, give} a dark red to purple color.

Example 4

5 g of polyacrylonitrile prepared in the presence of 0.5% methylenebisacrylamide are allowed to ^{swell in 150 cm 3 of} dimethylformamide. 10.5 g of NH ₂ OH · HCl and 7.5 g of anhydrous Na ₂ CO _{3 are then} added to this solution and the solution is heated to 80 ° C. for 3 hours. The reaction mixture is then poured into water and the insoluble polymer washed with warm water and methanol. The polymer absorbs ferric ions, which are exchangeable by treatment with concentrated HCl; this treatment can be repeated indefinitely.

Example 5

10 g of a copolymer of 64 mol percent acrylonitrile and 36 mol percent vinyl acetate (nitrogen content 13.8%) are dissolved in 100 cm ^{3 of} dimethylformamide. _{21 g of NH 2} OH-HCl and 15 g of anhydrous Na ₂ CO _{3 are} added to this solution. The solution will be

ίο heated to 75 ° C for 4 hours; the NaCl formed is filtered off with suction and the filtrate is precipitated with methanol. After thorough purification by dissolving in dimethylformamide and precipitating in methanol, a product with 16.9% N content is obtained. The reaction product is soluble in n / 10 NaOH and n / 10 HCl and, with FeCl _3, gives a dark red color.

Example 6

3 g of fibers made from a copolymer formed from about 60 mol percent vinyl chloride and 40 mol percent acrylonitrile are dissolved in 50 cm ^{3 of} dimethylformamide. 6.3 g of NH ₂ OH · HCl and 4.5 g of anhydrous Na ₂ CO _{3 are} added and the mixture is then added

Heated to 80 ° C for 2 hours. The reaction mixture is then filtered off with suction and the light-colored solution in methanol precipitated, the precipitate washed repeatedly with new methanol and dried in vacuo. That Polymers dissolves in aqueous HCl and NaO H solutions. Analysis: N = 16.5%; Cl = 9.6%.

If every nitrile group is converted into an amidoxime group and the chlorine atoms remain unchanged, the result is N = 16.9%; Cl = 27%.

Example 7

Ig staple fibers made from a copolymer, which is essentially formed from acrylonitrile and one or more monomers with characteristic infrared bands at 5.75 μ and 6 μ, is ^{dissolved in 10 cm 3 of} dimethylformamide. _{1.3 g of NH 2} OH.HCl and 1 g of anhydrous Na ₂ CO _{3 are added} to one part of this solution (A), _{and 0.65 g of NH 2} OH-HCl and 0.5 g of anhydrous Na _{2 are added} to the other part (B) CO ₃ added. The amount of hydroxylamine released in A is almost identical to the stoichiometric amount required to convert all of the nitrile groups; in B only half of this amount is released. Both samples A and B will be

Heated to 75 ° C. for 3 hours, filtered, precipitated in methanol and dried.

The modified product A dissolves in n / 10-HCl and n / 10-NaO H and is insoluble in dimethylformamide, B swells in n / 10 HCl, n / 10 NaOH and dimethylformamide.

Example 8

10 g of a copolymer consisting essentially of

about 47 mol percent acrylonitrile and 53 mol percent styrene is formed, are dissolved in 250 cm ^{3 of} dimethylformamide. The following additions are made to every 25 cm ^{3 of this solution:}

a) 0.250g NH ₂ OH-HCl and 0.190g Na ₂ CO ₃ ,

b) 0.500g NH ₂ OH-HCl and 0.380g Na ₂ CO ₃ ,

c) 1,000g NH ₂ OH-HCl and 0.760g Na ₂ CO ₃ ,
d) 4,200g NH ₂ OH-HCl and 3,000g Na ₂ CO ₃ .

The various test batches are heated to 75 ° C. for 2 hours. Then they are sucked off, knocked down, the precipitates washed in methanol and finally dried.

Table II
Characteristics of the various samples

acetone Solubility in n / 10 HCl N content attempt
No. + Dimethyl
formamide _ 8.1 Empty + attempt swells - a swells + - b swells + - C. - + - 9.3 d swells

- = insoluble + = soluble

Although neither the solution _{behavior nor the N 2} content can be used to determine the course of the reaction, the infrared spectrum clearly indicates the formation and increase in intensity of certain absorption bands, while the intensity of other bands falls simultaneously as a function of the amount of hydroxylamine used. During the reaction, the intensity of the CN band (4.5 μ) falls, as a new band arises and grows in the όμ region.

Example 9

10 g of a graft polymer of 45 g of polyvinylpyrrolidone with 160 cm ^{3 of} acrylonitrile (N content 23.4 ° / ₀ ) are dissolved in 100 cm ^{3 of} dimethylformamide, whereupon 10.7 g of NH ₂ OH-HCl and 8 g of anhydrous Na ₂ CO ₃ be added. The mixture is heated to 80 ° C. for 2 hours. The reaction mixture is then filtered off with suction, precipitated in methanol, washed with methanol and dried in vacuo. It can be dissolved in aqueous n / 10 HCl, in aqueous n / 10 NaOH and in dimethylformamide.

Example 10

1 g of polyvinyl cyanoethyl ether made from 22 g of high molecular weight polyvinyl alcohol and 100 cm ^{3 of} acrylonitrile (N content 14.35%) is dissolved in 20 cm ^{3 of} dimethylformamide, whereupon 2.1 g of NH ₂ OH.HCl and 1.5 g of anhydrous Na ₂ CO ₃ can be added. After about 3 hours of heating at 75 ° C., the reaction mixture is filtered off with suction and the filtrate is precipitated in methanol. The dried product contains 18.4% N and swells in NaOH and HCl solution. With ferric ions it gives a brown color.

Example 11

Viscose fibers are cyanoethylated according to the method of US Pat. No. 2,375,847. At the end of the reaction, the homogeneous solution is precipitated in methanol, centrifuged, dried, dissolved in acetone, reprecipitated in methanol, centrifuged and dried again. The high molecular weight product contains 11.9% N, which corresponds to 2.75 cyanoethyl residues per glucose unit. The infrared spectrum shows a characteristic CN band at 4.5 μ .

100 g of this cyanoethylated cellulose are dissolved in 2000 cm ^{3 of} dimethylformamide; 210 g of hydroxylamine chlorohydrate and 150 g of anhydrous Na ₂ CO _{3 are} added to this solution. The mixture is heated to 75 ° C. for 4 hours while stirring. The NaCl formed is filtered off with suction, the solution is precipitated in methanol, the precipitate is centrifuged and dried. N content = 15.9%. The modified product is soluble in n / 10 HCl; however, after standing for a few days, it becomes insoluble. The HCl solution gives a dark green color _{with FeCl 3.}

Example 12

Viscose fibers are superficially cyanoethylated according to US Pat. No. 2,375,847.

10 g of the dried fibers are mixed _{with 1500 cm * water, 21 g NH 2} OH-HCl and 15 g anhydrous Na ₂ CO _3. The mixture is heated to 75 ° C. for 3 hours, filtered off with suction, washed repeatedly with water and dried. The wet fibers give a dark green color _{with FeCl 3.} Polyacrylonitrile fibers can be treated in an analogous manner.

Example 13

10 g of a polymer containing CN groups prepared by cyanoethylating polyacrylamide oxime and 21 g of NH ₂ OH-HCl are dissolved in 200 cm ^{3 of} dimethylformamide. 15 g of anhydrous Na ₂ CO _{3 are} added to this solution. The whole is heated to 75 ° C. for 2 hours. The NaCl formed is filtered off with suction and the solution is precipitated in methanol, washed and dried. The product has the characteristics of amidoximes. Solubility in n / 10-NaOH and n / 10-HCl, color formation with FeCl ₃ . The infrared spectrum no longer shows any CN bands, but the typical C = NOH bands.

The product is insoluble in dimethylformamide.

Claims (3)

Patent claims: 1. Process for modifying high molecular weight organic substances containing nitrile groups an inorganic nitrogen base, characterized in that synthetic high molecular weight containing nitrile groups Substances or derivatives of natural or synthetic high-molecular substances containing nitrile groups treated with hydroxylamine. 2. The method according to claim 1, characterized in that as high molecular weight nitrile groups Substances polymers or copolymers of acrylonitrile are used. 3. The method according to claim 1, characterized in that as high molecular weight nitrile groups Substances cyanoethylated derivatives of natural or synthetic high molecular substances are used. Considered publications:
Swiss patents No. 290 305, 300887; U.S. Patent No. 2,497,526. A priority document was displayed when the registration was announced. © 809 748/462 1.59