DE1229244B - Manufacture of fibers or films from copolymers of acrylonitrile - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

DOIf

German class: 29 b-3/65

Number: 1229 244

File number: F 39820IV c / 29 b

Filing date: May 24, 1963

Opening day: November 24, 1966

From copolymers of acrylonitrile with vinylidene chloride with a chlorine content of 20 to 60% As is well known, technically valuable fibers or films can be obtained by converting their solutions into organic solvents in suitable dry or wet spinning equipment from nozzles in gases or Leaks liquids.

The fibers or films obtained are, however, already in a considerable extent in their manufacture discolor and even further discolour when exposed to heat or light. This reduces their value considerably.

It is known that chlorine-containing high molecular weight compounds can be protected against yellowing by adding stabilizers; so is z. B. the use of tin-containing organic compounds as stabilizers described. Antimony-containing compounds of the general forms Sb (SR ₃ ) and Sb (SR'COOR ") _{3 are also} known as stabilizers for chlorine-containing synthetic resins. In them, R denotes an alkyl, aryl or aralkyl radical, R 'an alkylene, arylene or ararylene radical and R "is hydrogen or a substituted or unsubstituted alkyl, aryl or aralkyl radical. Even the use of these classes of compounds does not have the desired effect to a sufficient extent and is in some cases associated with considerable odor nuisance.

The subject matter of the invention is a method of production of fibers or foils by spinning copolymers dissolved in organic solvents, obtained from acrylonitrile and vinylidene chloride with a chlorine content of 20 to 60% have been. The inventive method is characterized in that copolymers, the antimony compounds of the general formula

CH-S —Sb '

S-CH-R

O-Y

where R = hydrogen atom or alkyl group, X = CH ₂ OH or COOH group, Y = CH _? - or the CO group means, contained mixed in amounts of 0.1 to 5 percent by weight, based on the copolymer, dissolved in organic solvents and then spun as usual.

A number of compounds known as good polyvinyl chloride stabilizers are found in the manufacture of films and fibers from the manufacture of fibers or films
Acrylonitrile copolymers

Applicant:

Paint factories Bayer Aktiengesellschaft,

Leverkusen

Named as inventor:

Dr. Heino Logemann, Leverkusen-Schlebusch;

Dr. Hugo Malz, Leverkusen;

Dr. Heinz Rachwalsky, Dormagen;

Dr. Carlhans Süling, Leverkusen

mentioned chlorine-containing copolymers as insufficient. Except for their overwhelming effect the claimed antimony compounds still have the advantage that they are technically easily accessible, are practically indefinitely, non-toxic and odorless.

They can be produced by known methods; one sets z. B. Sb ₂ O ₃ or SbCl ₃ with «-Mercaptocarbonsäurenoderl-Hydroxy ^ -mercaptoalkanes or with mixtures of these mercapto components in a molar ratio of 1: 1 in an aqueous, mainly alkaline medium.

The stabilizers mentioned are used in an amount of 0.1 to 5% = preferably 0.5 to 1.5% based on polymer, used. They are added to the solvent if the acrylonitrile-vinylidene chloride copolymer is dissolved for spinning, or it is added to the polymer afterwards to manufacture too.

In certain cases, the solvent used is acetone, but generally one of the polar solvents customary for polyacrylonitrile, such as dimethylformamide, dimethylacetamide, ethylene glycol carbonate, dimethyl sulfoxide and others. The dissolution temperature is generally between +10 and +100 ⁰ C, preferably between +40 and + 80 ⁰ C, the polymer content of the solution between 5 and 35%.

example 1

10% solutions are obtained from a copolymer of 60 parts of acrylonitrile and 40 parts of vinylidene chloride made in dimethylformamide. Solution 1 does not contain any additional additive as a reference solution,

609 728/574

for solutions 2, 3 and 4, 0.5 or 1.0 or 1.5%, based on the polymer

S-CH ₂
CH ₂ -S-Sb (^

O-C = O
CH ₂ OH

added, with solutions 5, 6 and 7 each 0.5, 1.0 and 1.5% dibutyltin dilaurate. The solutions will be Aged for 16 hours in thermostats at 80 ° C. From the aged solutions are placed on glass plates with A pulling device, foils of the same thickness as possible, are drawn in a drying cabinet with air suction be dried at 50 ° C overnight.

The films are stripped from the glass plates, clamped onto glass frame, washed 1 hour in water at 7O ⁰ C and dried again. They are then aged for 4 or 8 hours in a drying cabinet with moving air at 140 ° C. The light absorption of the more or less yellow-brown discolored films is measured in a General Electric spectrophotometer. Since the thickness of the foils deviates a little from the desired thickness of 50 μ,

ίο are found the permeability values with Corrected these minor deviations with the help of Beer’s Law. When measuring the absorption is not measured against a clear, neutral film, so the maximum is the achievable light transmission about 92%.

CH ₂ OH O-C = O CH ₂ OH 0 -C = O CH ₂ OH Light transmission ( ⁽ 450 ηιμ at A = 550 πιμ 600 ηιμ / ο) 450 πιμ beil = 550πιμ 600 πιμ For solution 3 with 1% For solution 4 with 1.5% For solution 5 with 0.5% after 4 hours of aging at 140 ° C 22.1 500 ηιμ 53.6 64.7 0.8 500 πιμ 15.8 30.8 / S - CH ₂ ζ S - CH ₂ Dibutyltin dilaurate 39.5 5.1 CH ₂ -S-Sb (^ CH ₂ -S-Sb (^ For solution 6 with 1% 400 ΐημ after 8 hours of aging at 140 ° C With solution 1 without addition Dibutyltin dilaurate 8.1 (Comparison) For solution 7 with 1.5% 56.6 79.8 84.7 400 ΐημ 20.2 5.47 69.7 For solution 2 with 0.5% Dibutyltin dilaurate 71.4 0.4 40.2 . S - CH ₂ CH ₂ -S-Sb ^ 34.5 ^ O-C = O 63.4 82.6 86.3 6.9 23.0 61.1 72.2 74.8 43.9 42.6 63.4 82.6 86.5 7.5 28.9 65.5 75.8 76.4 49.9 44.1 39.6 67.4 75.3 4.3 30.7 46.5 56.4 15.0 31.6 59.0 67.1 11.0 5.7 31.7 46.3 20.5 47.5 16.7 35.1 56.1 61.8 2.7 16.5 25.3 15.0 47.7 1.0 8.3 19.3 1.7 0.8

The light transmission of the aged foils is 0.5% antimony-tri-n-lauryl mercaptide Sb (SC ₁₂ H ₂ S) ₃ , in the case of the solution 3 stabilized with the antimony complex 1.5% thereof, in the solutions 4 and 5 foils much higher and remains 0.5 or 1.5% for longer

sustained thermal stress better preserved , S - CH ₂

than those stabilized with dibutyltin dilaurate. In the same proportion turn out to be also with small

thermal stresses according to the invention 60 'O - C = O

stabilized foils than much purer white. CH ₂ OH

τ. . . . - for solutions 6 and 70.5 or 1.5%

ΰ eispxex ^

CHo-S-

From a copolymer of 60 parts of acrylonitrile

and 40 parts of vinylidene chloride are 10% strength 65 CH ₂ -S-Sb.

solutions made in dimethylformamide. Solution 1 I.

does not contain any other additive as a comparison solution; CH ₂ OH

for solution 2, based on the polymer, are added.

ο

CH

The solutions are heated in accordance with Example 1, 4 or 8 hours at 140 ° C and aged for 16 hours at 80 ⁰ C in the thermostat, then measured. You can find a light permeability in films are drawn from them, these are washed, percent.

CH ₂ -S-Sb (^ Light transmission ( ⁰ J ₀ ) 450 ηιμ 500 ηιμ 550 πιμ 600 πιμ nacl ι 8 hours aging at 14O ⁰ C
is called λ = 500 πιμ 550 πιμ 600 ηιμ after aging at 140 ^° C. for 4 hours
is called λ = 33.6 51.2 64.6 73.4 400 ηιμ 450 πιμ 5.4 16.4 31.3 I O-C = O 400 ηιμ 0.3 0.9 With solution 1 without addition CH ₂ OH 15.5 29.7 45.6 55.3 64.1 22.4 37.8 40.5 (Comparison) For solution 5 with 1.5% 40.0 49.9 56.3 63.9 2.6 8.8 27.9 39.5 48.9 For solution 2 with 0.5% / O y ~ -n _z 13.5 6.2 14.8 For solution 3 with 1.5% CH ₂ -S-Sb (^ 26.3 Sb (SC ₁₂ H ₂₅ ) ₃ For solution 4 with 0.5% I ^ 0-C = O 48.9 60.8 68.0 73.2 31.4 46.2 57.6 ς ΓΉ CH ₂ OH 5.3 15.2 For solution 6 with 0.5%
ς γη 31.6 CH ₂ -S-Sb ' I 0-CH ₂ 55.7 67.8 74.5 79.0 49.4 62.8 71.6 CH ₂ OH 12.8 30.4 For solution 7 with 1.5% 37.0 / S-CH ₂ CH ₂ -S-Sb (^ 51.0 68.4 76.8 82.2 30.0 49.0 64.7 3.8 11.9 I 0-CH ₅ 29.0 CH ₂ OH 54.0 72.0 77.2 84.8 46.5 64.0 74.8 8.5 23.7 30.3

The transparency of the films is both after aging for 4 hours and after Hours when using the ring-shaped antimony complexes significantly higher than when using the Antimony trimercaptids as a stabilizer.

5o

Claims (1)

Claim: Process for the production of fibers or films by spinning in organic Copolymers dissolved in solvents, consisting of acrylonitrile and vinylidene chloride with a chlorine content from 20 to 60% have been obtained, characterized in that one Copolymers, the antimony compounds of general formula
R. CH-S —S .S —CH-R ¹ OY where R = hydrogen atom or alkyl group, X = CH ₂ OH or COOH group, Y = CH ₂ - or the CO group, in amounts of 0.1 to 5 percent by weight, based on the copolymer, mixed in, in organic Solvents and then spun as usual. Considered publications:
Austrian patent specification No. 207 036. When the application was announced, a test report (comparative example) was displayed. 609 728B74 11.66 © Bundesdruckerei Berlin