DE1210559B - Stabilizer mixtures for homo- or copolymers of alkylene oxides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08g

German KL: 39 b-22/10

Number: 1 210 559

File number: F 42644IV c / 39 b

Filing date: April 18, 1964

Opening day: February 10, 1966

Homo- and copolymers of alkylene oxides are known to be, like all polyethers, by light and oxygen in the air decomposes to a greater or lesser extent. Therefore, they must be processed or used before they can be used be stabilized. It is known as stabilizers for e.g. B. polypropylene oxide aromatic To use amines or phenols. However, such stabilizers are not enough to make one Prevent degradation in the presence of light and heat.

The subject of the invention is the use of a 3-component mixture of 0.1 to 5 percent by weight one or more compounds of the general formula (I) and each 0.01 to 5 percent by weight one or more compounds of the general formulas (II) and (III), all percentages are based on the polymer, with the formulas

I. Nickel complexes of monoazo dyes

COOH

II. HO

III.

C (CHs) ₃

CO-NR-Ri

OH

C (CHs) ₃

R ₄ -Sj ₁ -R ₅

Stabilizer mixtures for homo- or
Copolymers of alkylene oxides

Applicant:

Farbwerke Hoechst Aktiengesellschaft

formerly Master Lucius & Brüning,

Frankfurt / M.

Named as inventor:

Dr. Otto Mauz, Niederhofheim (Taunus);

Dr. Joachim Ribka, Offenbach / M.-Bürgel

represent; in the general formulas, R = alkyl, aryl or heterocyclic radical; Ri = alkyl, aralkyl, cycloalkyl, aryl or heterocyclic radical; A is an —S— or —CH2 — group; R2 and R _{3 are} identical or different alkyl radicals having 1 to 4 carbon atoms; η is an integer from 1 to 4; R4 and R5 are identical or different alkyl radicals with z. B. 4 to 30 carbon atoms or the group

- (CH ₂ ) _m - COO • R ₆

where Re is an alkyl radical having 4 to 30 carbon atoms and m is an integer from 1 to 4, for stabilizing homo- or copolymers of alkylene oxides that are already polymeric against degradation by light and heat.

Protection is not given here for the use of the whole mixture, not of its individual components desired.

Examples of compounds of the general formula I include:

The nickel complexes obtained by coupling diazotized anthranilic acid or its in the benzene nucleus substituted derivatives with acetoacetamides of the formula

CH ₃ • CO • CH ₂ • CONH • A

wherein A is an alkyl radical, for example a methyl, propyl, butyl, nonyl, dodecyl, oleyl or Stearyl radical, a benzyl, cyclohexyl, optionally substituted phenyl or naphthyl radical or a 5- or 6-membered heterocyclic ring, for example a pyrazole, imidazole, triazole, Thiazole, oxazole, thiodiazole, oxdiazole, pyrimidine, pyridine, quinoline, indazole, benzimidazole, benzthiazole or benzoxazole ring means available azo dyes.

Furthermore, the nickel complexes of dyes come into consideration, which are diazotized by coupling Anthranilic acid or its derivatives with other acyl acetic acid amides, for example propionyl, Butyryl, benzoyl or furoyl acetic acid amides are obtained.

609 507/357

Examples of general compounds include:

Bis- (4-hydroxy-2-methyl-5-tert-butyl-phenyl) -

methane,
Bis- (4-hydroxy-2-propyl-5-tert-butyl-phenyl) methane,

Bis- (4-hydroxy-2,5-di-tert-butyl-phenyl) -methane, bis- (4-hydroxy-2-methyl-5-tert-butyl-phenyl) -

sulfide,
Bis (4-hydroxy-2-propyl-5-tert-butyl-phenyl) -

sulfide,
Bis (4-hydroxy-2,5-di-tert-butyl-phenyl) sulfide.

Examples of organic sulfur compounds of the general formula III include: di- (dodecyl) sulfide, Di (octadecyl) sulfide, di (dodecyl) disulfide, di (octadecyl) disulfide, di (dodecyl) trisulfide, Di- (octadecyl) -trisulfide, di- (dodecyl) -tetrasulfide, di- (octadecyl) - tetrasulfide, thiodiglycolic acid dodecyl ester, thiodipropionic acid octadecyl ester, thio dibutyric acid dodecyl ester, Trisulfide (diacetic acid octadecyl ester), tetrasurfide (diacetic acid octadecyl ester),

The homo- and copolymers to be stabilized are, as usual, by polymerizing saturated alkylene oxides, such as ethylene oxide, propylene oxide, also substituted epoxides, such as B. epichlorohydrin, perfluoropropylene oxide and l-chloro-3,4-epoxybutane, also cycloaliphatic Epoxides, such as cyclohexene oxide, also epoxy ethers, such as methyl and phenyl glycidyl ethers, or by copolymerization of saturated with unsaturated epoxies, such as allyl glycidyl ether, o-Allylphenylglycidäther, Glycydacrylat, Vinylcyclohexenmonoepoxyd, Cyclohexene oxide, butadiene monoxide, 1,2-epoxyhexene-5, 1,2-epoxycycloocten- (5), produced in the presence of known ionic catalysts.

The addition to the already highly polymeric polymers is carried out in the customary manner. That Addition before or during the polymerization should not be protected here.

The polyalkylene oxides stabilized according to the invention can be used in a wide variety of ways, e.g. B. to Manufacture of moldings, films and fibers.

The homopolymers and copolymers listed above can also be used in suitable solvents and swelling agents be dissolved or swollen, the solutions or swellings having a solid content from about 20 to 30%. Suitable solvents or swelling agents are, for. B. named: Dimethylformamide, tetramethylene sulfone, dioxane, methanol, benzene and other aromatics, as well Chlorinated hydrocarbons and mixtures of two and three of the solvents or swelling agents mentioned.

The solutions or swellings of the polymers stabilized according to the invention can also be added other substances are added, such as active or inactive carbon blacks or light-colored fillers, dyes or Pigments, extending oils, lubricants, etc.

In the stabilizer system to be used according to the invention contained individual compounds II and III, which are known as stabilizers for other polymer classes, exercise on polymers of Alkylene oxides do not have any stabilizing effect. The compounds of the formula I are also not Stabilizers for polymeric alkylene oxides. It was

Formula II therefore to a great extent surprising that it is possible to use a combination of these on their own taken ineffective compounds to sharpen a catalyst system, the polymers of alkylene

5 oxides in an excellent way against the effects of Protects light and heat. Another advantage of the stabilizer system to be used according to the invention consists in the fact that, as a result of the synergistic effect of the components, the concentration the phenolic component can keep so low that no discoloration of the polymers, especially during processing at high temperatures.

To test the stability of the polyalkylene oxides stabilized according to the invention, the following was carried out procedure.

example

On a roller mill, a roller temperature of about 40 ° C. is carried out using a copolymer a mixture of 92.5 mol percent propylene oxide and 7.5 mol percent allyl glycidyl ether manufactured with the following composition:

Parts by weight

Copolymer 100.0

Thiourea 1.0

Silica, active 15.0

Zinc oxide 7.5

Dipentamethylene thiuram tetrasulfide 5.0

2-mercaptobenzothiazole 0.75

Kronos-wise 3.0

132.25

100 parts by weight of this mixture are dissolved or made into a paste in 400 parts by weight of methanol and a mixture of 2 percent by weight of the compounds mentioned in the table according to general formula I and 0.5 percent by weight bis (4-hydroxy-5-tert-butyl-2-methyl-phenyl) sulfide and 0.5 weight percent di (octadecyl) disulfide 'added as heat stabilizers. This solution or this gel is spun using water as the precipitation bath liquid under the following conditions and then networked in a heated shaft:

Spinning temperature 20 ° C

Delivery rate 0.2 g / min.

Nozzle 6/300 μ

Titer 6/200 den

Temperature of the precipitation bath 20 ° C

Residence time in the felling bath .. '. 60 seconds
Crosslinking temperature 16O ⁰ C
Duration of networking in

a heated shaft 60 seconds
Take-off speed .... 5 m / min.
Post-vulcanization on the

Coil 120 seconds /

160 ° C hot air

The properties of the fibers after 80 hours of exposure with the Xenotest high-speed imagesetter result from the following table.

5 6

The nickel salts of the following compounds have proven to be particularly effective:

COO · Ni / 2

/ CO - CH ₃

1.

n = n — ch:

< • Ni / ₂ CH ( ^N C0 -NH- CwHffi O N = N- Λ / 2. / CO - CH ₃
^X CO - NH - _c / N \ • Ni / 2 CH ( "M N = N- JN 3. / CO - CH ₃
\ cr \ > JTT CH • Ni / 2 CH C Ks \ J IN 11 Ly
Μ = / N = N- Il
N
NT A. COO
I. CO - CH ₃ 4th i- /
^X CO —NH- N COO i- COO

5.

COO ■ Ni / a

N = N-CH

CO-

-CO-NH-N-

Il
-c

-CH

Il

CH

-NH '

Without a connection

according to the general formula I Compounds according to the general formula I

a)
Connection according to

mentioned above
formula 1

b) Connection according to

Formula 2 above

Relative tear strength in% of the initial tear strength after 80 hours of exposure with the Xenotest high-speed imagesetter *)

Relative residual elongation at break in% of the initial elongation at break after exposure to light for 80 hours the Xenotest high-speed imagesetter

*) Temperature 45 ⁰ C, relative humidity 30%. embrittled,
no longer measurable

embrittled,
no longer measurable

27%

38%

31%

41%

Claims (1)

Claim: Use of a 3-component mixture of 0.1 to 5 percent by weight of one or more Compounds of the general formula (I) and each 0.01 to 5 percent by weight of one or more Compounds of the general formula (II) and (III), all percentages are based on the no Polymers based, with the formulas I. Nickel complexes of monoazo dyes R.
COOH ^ ₀ = N-CH-CO-NR-Ri R ₃ II. HO C (CHa) ₃
III. R ₄ -S _n -R ₅ C (CHs) ₃ 65 represent - in the general formulas, K = optionally substituted benzene or Naphthalene residue; R = alkyl, aryl or heterocyclic radical; Ri = alkyl, aralkyl, Cycloalkyl, aryl or heterocyclic radical; A is an —S— or —CH2— group, R2 7 8 and R3 are identical or different alkyl radicals with atoms and m is an integer from 1 to 4 1 to 4 carbon atoms; η indicates an integer -, to stabilize already polymeric from 1 to 4; R4 and R5 are identical or different 'homo- or copolymers of Alkyl radicals with 4 to 30 carbon atoms or alkylene oxides against degradation by light and the group 5 heat. ⁶ 'Publications considered: wherein R _{6 is} an alkyl radical having 4 to 30 carbon- Deutsche Auslegeschrift No. 1 101 016. 609 507/357 2.66 © Bundesdruckerei Berlin