DE1173253B - Process for the production of vinylidenecyanide copolymers - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school KL: C08f

German class: 39 c - 25/01

Number: 1173 253

File number: F 36909IV d / 39 c

Filing date: May 25, 1962

Opening day: July 2nd, 1964

• It is known to use vinylidenecyanide in inert solvents with vinyl or acrylic monomers To polymerize mixed polymers with an alternating chain structure. Prerequisite for this polymerization is that the interpolymerization parameters of the monomers are those for an alternating Copolymerization required values of the equation

d [Mi] [Aft] η [Mi] + Uf [M ₂ ] [M ₂ ] T ₂ [M ₂ ] + [M ₂ ]

(M. F. Lewis, C. Walling, Journ. Of American Chemical Society, 70, p. 1519 [1948]). However, it is difficult to produce such copolymers, which, when processed into fibers or threads, have good mechanical properties, can be dyed, thereby severely limiting the value of such products.

It has already been proposed that maleic anhydride be used to improve the dyeability of such copolymers polymerize with. U.S. Patent 2,716,106 discloses a method of manufacture of terpolymers of vinylidenecyanide with vinyl acetate and other monounsaturated Connections described. By incorporating the compounds mentioned in this patent specification, however, the strictly alternating structure of the polymer is so disturbed that a lowering of the melting point and a loosening of the fiber structure occurs. Furthermore, it has already been proposed that Colorability of copolymers of vinylidenecyanide with a vinyl or acrylic compound To improve the polymerisation of itaconic anhydride.

There has now been a process for the production of copolymers from vinylidenecyanide, a vinyl or acrylic compound and a third monomer by radical polymerization Polymerization triggers in organic, anhydrous, the ionic homopolymerization of the Vinylidenecyanide-preventing solvents found, in which then colorless, alternately structured, easily dyeable, ternary copolymers with good mechanical properties are produced, if the third monomer is vinyl sulfonic acid or vinyl phosphonic acid in amounts of up to 10 percent by weight, based on the total concentration of the monomers, is used.

It is known that vinyl sulfonic acid and, to a lesser extent, vinyl phosphonic acid in polymers can cause discoloration as a result of resinification reactions. It was therefore over-

Process for the production of
Vinylidenecyanide copolymers

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning, Frankfurt / M.

Named as inventor:

Dr. Wolfgang Göltner, Kriftel (Taunus),

Dr. Hans Hoyer, Frankfurt / M.-Höchst

surprising that the copolymers obtained by the process of the invention are obtained colorless, when the amount of vinyl sulfonic acid or vinyl phosphonic acid is up to 10 percent by weight of the Total amount of all monomers.

Advantageous copolymers of 40 to 60 percent by weight are obtained by the process according to the invention Vinylidenecyanide, 60 to 40 percent by weight of a vinyl or acrylic compound and up to obtained to 10 percent by weight vinyl sulfonic acid or vinyl phosphonic acid.

Suitable vinyl compounds are, for example, the vinyl esters of aliphatic or aromatic carboxylic acids, such as vinyl acetate, vinyl chloroacetate, vinyl propionate and vinyl benzoate, or one or more times unsaturated hydrocarbons, such as ethylene, propylene, butylene, butadiene, styrene or their derivatives, z. B. α-methylstyrene, chloromethylstyrene. As acrylic compounds can nitriles of acrylic and methacrylic acid or their esters with primary, saturated, monohydric, aliphatic alcohols containing up to 4 carbon atoms can be used. The copolymers with vinyl acetate have particularly favorable properties.

Acetonitrile and glacial acetic acid are particularly suitable as solvents. But all can also be organic Solvents are used if they are vinyl sulfonic acid or vinyl phosphonic acid dissolve and prevent the ionic homopolymerization of vinylidenecyanide. Also a mixture several solvents can be used.

The properties of the copolymers are determined by the concentration of the monomers in the Polymerization solution affected. The concentration of the monomers in the reaction mixture depends on them Solubility dependent, but it can fluctuate within wide limits.

409 628/354

In general, a ratio of 1 part by weight of polymerization with vinyl compounds is not very suitable.

of the monomer mixture to 0.3 to 5 parts by weight of Neten monomers a disturbance of the alternating

Solvent advantageous. Chain build-up is to be expected. As a result of this

The vinyl sulfone disorder used as the third component must be accompanied by a reduction in the mechanical

or vinylphosphonic acid can be seen at the beginning or not until 5 and physical properties are calculated

be added in the course of the polymerization. A part can also be presented and the rest in the course be added dropwise to the reaction. In this procedure, the acid is advantageously used in one of the above Solvent added.

The polymerization can be triggered by the reaction triggers customary in polymerization technology, such as peroxides, percarbonates or initiators of the type of azo compounds. Redox systems are also suitable for this, provided they does not initiate an ionic homopolymerization. Combinations of the compounds mentioned can also be used to add. It is particularly advantageous to do so, but it is not observed.

Particularly surprising is the good thermal stability of the fibers or threads produced from the copolymers, which can withstand processing ^{temperatures of up to 230 °} C. without discoloration being observed.

The process according to the invention can also be carried out continuously using suitable equipment carry out.

example 1

A solution is extracted in a stirred vessel equipped with a condenser, inlet tube and thermometer

Use of azoisobutyric acid dinitrile.

The reaction triggers can initially or 20 7.8 parts vinylidenecyanide, 18 parts vinyl acetate,

can also be added during the reaction. In 1.65 parts of vinyl sulfonic acid and 0.22 part of azoisobutyric acid dinitrile held at 40 ° C. for 24 hours in 6.9 parts of glacial acetic acid while stirring and passing nitrogen through. The approach is then with

per mole of monomer mixture added. This 25 50 parts of absolute ether added, the polymer

The range can be exceeded or fallen below, because it is sucked off with ether, then with alcohol

washed and dried in vacuo at room temperature.
The yield of colorless polymer is

in the latter case it is advantageous to use the initiator in Add solution dropwise. The initiators are used in the usual amounts, for example 1 to 100 millimoles

the choice of initiator concentration on the polymerization temperature, depends on the type of monomers and also on the solvent.

The reaction temperature must be the given 3 ° 11 parts. Reaction conditions, e.g. B. the effectiveness of the polymerization ^{trigger and the constitution of ητβ1}

Monomers are adapted. In general it is
most favorable temperature range between 30 and
60 ⁰ C, but it can be advantageous below, z. B. color 35 tones, at 0 to 20 ⁰ C, or above this range, z. B.
at 70 to 80 ⁰ C to work. So it is appropriate at
the use of styrene the polymerization
to run below 30 ⁰ C. To get the

ψα == 1.82; N _Kj = 16.7%; S = 0.91%.

The product can be combined with basic dyes and disperse dyes in deep, luminous

Example 2

In an apparatus described in Example 1, a solution of 7.8 parts of vinylidenecyanide, combination of vinylidenecyanide — vinyl acetate — vinyl 40, 18 parts of vinyl acetate, 0.85 parts of vinylsulfonic acid, sulfonic acid is used to avoid discoloration, 0.22 part of azoisobutyric acid dinitrile in 6, 9 parts the temperature of 40 ⁰ C advantageous.

For work-up, the reaction mixture is further, the ionic homopolymerization of the Vinylidenecanids preventing solvents such as glacial acetic acid, ether, ethyl acetate or benzene, added, whereby the polymerization is interrupted and the copolymer is obtained in a filterable form. That Copolymer is suctioned off and washed with the solvent used until it is freed from the last residues of vinylidenecyanide. After that, alcohol or water is used for the dem Vinylphosphonic acid or vinylsulfonic acid still adhering to the polymers was washed out.

The 55 manufactured according to the method of the invention
th copolymers have an alternating
Chain structure and good mechanical properties.
With basic dyes and disperse dyes
they can be colored in deep and brilliant tones. The colorations are distinguished by good dinitrile, dissolved in 6.9 parts of glacial acetic acid, lightfastness with stirring. and passing nitrogen through to 40 ^° C. for 24 hours

The copolymers produced according to the invention, in particular those using Vinyl acetate produced can be spun into fibers or threads with excellent properties.

The beneficial effect of vinyl sulfonic acid or vinyl phosphonic acid is surprising because through the installation of a third, alternating Co-glacial acetic acid 24 hours at 40 ° C while passing through stirred by nitrogen. The reaction mixture is worked up as in Example 1. 13 parts of a colorless polymer are obtained.

_ητ * = 2.78; Nkj = 16.8%; S = 0.62%.

This polymer can also be colored very well with basic dyes.

A 15% solution of the product in dimethylformamide has a viscosity of 257 poises and can be made into threads and fibers with good mechanical properties Process properties.

Example 3

As in Example 1, a mixture of 7.8 parts vinylidenecyanide, 18 parts vinyl acetate, 0.42 parts Vinyl sulfonic acid and 0.22 parts of azoisobutyric acid

held. Then, as described in Example 1, worked up.
Yield: 14 parts.

ητ, ι = 3.68; N _K j = 15.6%; S = 0.34%.

The colorless polymer can be easily dyed with basic dyes and disperse dyes.

Example 4

78 parts of vinylidenecyanide, 172 parts of vinyl acetate, 8.5 parts of vinylsulfonic acid and 4 parts of azoisobutyric acid dinitrile are dissolved in 62 parts of glacial acetic acid. The batch is stirred ^{at 40 °} C. while passing in nitrogen. A solution of 8.5 parts of vinyl sulfonic acid in 25 parts of glacial acetic acid is slowly added dropwise over the course of 8 hours. After a reaction time of 8 hours, 70 parts of a colorless copolymer could be isolated by the work-up method mentioned in Example 1.

ΨΛ = 3.18; N _Kj = 16.9%; S = 0.58%.
The product can be dyed very well.

Example 5

A solution of 468 parts of vinylidene cyanide, 1032 parts of vinyl acetate, 25 parts of vinylphosphonic acid and 12 parts of azobisisobutyronitrile in 1272 parts glacial acetic acid is kept 11 hours at 4O ⁰ C with stirring and passing through nitrogen. It is then worked up as in Example 1.

Yield: 780 parts.

_ψΛ = 7.13; N _K j = 16.4%; P = 0.4%.

Example 6

In the apparatus used in Example 1, 78 parts of vinylidene cyanide, 172 parts of vinyl acetate, 25 parts of vinylphosphonic acid and 2 parts of azoisobutyric acid dinitrile are dissolved in 52 parts of glacial acetic acid. The batch is kept at 40 ° C. for 7 hours while nitrogen is passed through. Then 250 parts of anhydrous ether are added to the batch and the polymer formed is filtered off with suction. This is then washed with ether and then with alcohol and dried in vacuo.
Yield: 133 parts.

, "J = 7.03; N _K j = 14.9%; P = 0.6%.

A 12% solution of the colorless product in dimethylformamide has an absolute viscosity of 356 poises. It can be spun and gives threads with good mechanical properties that in deep, luminous tones with both basic dyes and disperse dyes let stain. The dyeings have good lightfastness.

Claims (1)

Claim: Process for the production of copolymers from vinylidenecyanide, a vinyl or Acrylic compound and a third monomer, by polymerization under the action radical polymerization trigger in organic, anhydrous, ionic homopolymerization of the vinylidenecyanide preventing solvents, characterized in that vinylsulfonic acid or as the third monomer Vinylphosphonic acid in amounts up to 10 percent by weight, based on the total concentration of the monomers. Considered publications:
U.S. Patent No. 2,716,106. 409 628/354 6.64 © Bundesdruckerei ßerliti