DE1210179B - Stabilizer mixture for homo- or copolymers of alkylene oxides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

int. CL:

C08g

German class: 39 b - 22/10

Number: 1210179

File number: F 43494 IVc / 39 b

Filing date: July 18, 1964

Opening day: February 3, 1966

It is known that homo- and copolymers of alkylene oxides, like all polyethers, under the action subjected to more or less strong decomposition reactions by light and atmospheric oxygen and must therefore be stabilized before they are processed or used. It was too already proposed as stabilizers for e.g. polypropylene oxide aromatic amines or phenols to use. However, such stabilizers are not sufficient to cause degradation in the presence to prevent light and heat.

The subject of the invention is the use of the three-component mixture of 0.1 to 5 percent by weight on one or more nickel complexes of compounds of the general formula I and each 0.01 to 5 percent by weight of one or several compounds of the general formulas II and III, all percentages are given in based on the polymer, wherein

C - NH - CO - Alk

HO

C (CH ₃ ^

OH

C (CH ₃ ) S

II Stabilizer mixture for homo- or copolymers of alkylene oxides

Applicant:

Farbwerke Hoechst Aktiengesellschaft formerly Master Lucius & Brüning, Frankfurt / M.

Named as the inventor

Dr. Otto Mauz, Niederhofheim (Taunus); Dr. Ulrich Dreyer, Offenbach / M.-Bürgel

Examples of nickel complexes of compounds of the general formula I include: Nickel complexes des

3-AcetyIamino-l, 2,4-triazoles,
S-Propionylammo-l ^^ triazoles, 3-Caproylamino-l, 2,4-triazoles, 3-LauroylaBiino-l, 2,4-triazoles, 3-Myristoylamino-l, 2,4-triazoles, 3-Palmitoylammo-l , 2,4-triazoles, 3-stearoylamino-1,2,4-triazoles, 5-methyl-3-IarfroyIamino-1,2,4-triazoles, 5-ethyl-3-pahnitoylamino-1,2,4-triazoles , llil ^^ il

K4 Or K ₅ Ui

means - in the general formulas Ri means Hydrogen or a lower alkyl radical, Alk one Alkyl radical having 1 to 20 carbon atoms; A a

- S— or —CH2—, but preferably eme

- S - group, R2 and Rs identical or different alkyl radicals with 1 to 4 carbon atoms, but preferably with one carbon atom; η is a 4a integer from -1 to 4, Ri and R5 are identical or different alkyl radicals with z. B. 3 to 30, preferably 8 to 20 carbon atoms or the group

- (CH ₂ ) _m - COO ■ R ₆ , where Rs is an alkyl radical having 4 to 30 carbon atoms and m is an integer from 1 to 4 -, for stabilizing homo- and copolymers of alkylene oxides that are already polymeric against degradation by heat and Light.

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

pyp
5-Pyopyl-3-steailammo-1,2,4-triazo] s.

Examples of compounds of the general formula II include:

Bis- {4-hydroxy-2-methyl-5-tert-buty! -Phenyl>

methane,
Bis- (4-hydFOxy-2-propyI-5-tert-butyl-phenyl) -

methane,
Bis- (44iydroxy-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 ^ -di-tert-butyl-phenyl) -sulfide.

Examples of organic sulfur compounds of the general formula IH are:

Di (docecyl) sulfide,
DHoctadecyQ sulfide,
Di (dodecyl) disulfide,
Di- (octadeeyl) disulfide,

609 503/416

Di- (dodecyl) trisulfide,

Di (octadecyl) trisulfide,

Di-CdodecylHetrasulfide,

Di (octadecyl) tetrasulfide,

Dodecyl thio-diglycolate,

Octadecyl thio-dipropionate,

Thio-dibutyric acid dodecyl ester,

Trisulfide (octadecyl diacetate) j

Tetrasulfide- ^ diacetic acid octadecyl ester).

The polymers to be stabilized according to the invention are homopolymers and copolymers of alkylene oxides in question. The homo- and copolymers are made by polymerizing saturated alkylene oxide, such as ethylene oxide, propylene oxide, also substituted epoxides, e.g. Epichlorohydrin, perfluoropropylene oxide and 1-chloro-3,4-epoxybutane, also cycloaliphatic epoxides, such as cyclohexene oxide, further epoxy ethers, such as methyl and Phenylglycidäther, or by copolymerization of saturated with unsaturated epoxies, such as for example allyl glycidyl ether, o-allylphenyl glycidyl ether, Glycidacrylat, Vinylcyclohexenmonoepoxid, Cyclohexenoxid, Butadienemonoxyd, 1,2-Epoxyhexen-5, 1,2-Epoxycycloocten- (5), produced in the presence of known ionic catalysts. The polyalkylene oxides stabilized according to the invention can be used in a variety of ways, e.g. B. for the production of moldings, films and fibers.

The homopolymers and copolymers listed above can also be dissolved or swollen in suitable solvents or swelling agents, the solutions or swelling agents having a solids content from about 20 to 30%. Suitable solvents or swelling agents are, for example: Dimethylformamide, 1 etramethylene sulphon, dioxane, Methanol, benzene and other aromatics, also chlorinated hydrocarbons and mixtures of two and three of the solvents or swelling agents mentioned.

The solutions or swellings of the copolymers stabilized according to the invention from saturated and unsaturated epoxides can be added to crosslinking compounds. Such Crosslinkers are z. B. sulfur accelerator systems, organic peroxides or other substances that form free radicals under crosslinking conditions such as Azodiisobutyric acid mitril or azodicarboxylic acid diamide.

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 black or light-colored fillers, dyes or Pigments, extending oils, lubricants, etc.

example

On a rolling mill at about 40 ⁰ C roll

tempeiatar using a copolymer a mixture of 92.5 mol percent propylene oxide and 7.5 mol percent allyl glycidyl ether made of the following composition:

Parts by weight

Copolymer 100.0

ίο thiourea 1.0

Silica, active 15.0

Zmkoxyd 7.5

Dipentamethylene thiuram tetrasulfide 5.0

2-mercaptobenzothiazole 0.75

»5 Kronosweiß ® (white pigment with

about 25% titanium dioxide content) ... 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 of the general formula I and 0.5 percent by weight bis (4-hydroxy-5-tert-butyl-2-methylphenyl) sulfide 25. and 0.5 percent by weight di (octadecyl) disulfide as Heat stabilizers added. This solution or this gel is using water as Spun precipitation bath liquid under the following conditions and then in a heated one Networked shaft:

Spin temperature 20 ⁰ C.

Delivery rate .. - 0.2 g / min.

Nozzle 6/300 μ

Titef: ■ 6/200den

Temperature of the precipitation bath 20 ° C

Dwell time in the felling bath. 60 seconds

Crosslinking temperature 160 ⁰ C

Duration of networking in one

heated shaft 60 seconds

Take-off speed 5 m / min.

Post-vulcanization on the coil .. 120 seconds /

160 ° C hot air

The following three stabilizers were used for testing:

a) 3-Caproy.lammo-l, 2,4-triazole, nickel complex,

b) 3-stearylamino-l, 2,4-triazole, nickel complex,

c) 5-propyl-3-stearoylarnino-l, 2,4-triazole, Nickel complex.

The properties of the fibers after 100 hours of exposure with the Xenotest high-speed exposure resulted from the following table:

Without a nickel complex
a connection of the
general formula I.

With a. Nickel complex of a compound of the general formula I.

a) b) c)

Relative residual tensile strength in% of the initial tensile strength after 100 hours of exposure to the Xenotest high-speed imagesetter *)

Relative residual elongation at break in ° / q of the initial elongation at break after 100 hours of exposure with the Xenotest high-speed imagesetter *)

*) Temperature 45 ° C, relative humidity 30 ° / ₀ .

brittle,
no longer measurable

embrittled,
no longer measurable

38%

58%

42%

60%

47%

67%

Claims (1)

Claim: Use of the three-component mixture of 0.1 to 5 percent by weight of one or several nickel complexes of compounds N C —NH — CO —Alk HO Il Il Ri-C N of the general formula I and 0.01 to 5 percent by weight each of one or more compounds of the general formulas II and III, all percentages are based on the polymer related, where C (CHs) ₃ OH C (CHs) ₃ R4 S _re R5 III II means - in the general formulas, Ri means hydrogen or a lower alkyl radical, Alk an alkyl radical having 1 to 20 carbon atoms; A is an —S— or —CH ₂ —-, but preferably an —S— group, R2 and R _{3 are} identical or different alkyl radicals with 1 to 4 carbon atoms, but preferably with one carbon atom; η is an integer from 1 to 4, R4 and R5 are identical or different alkyl radicals with z. B. 3 to 30, preferably 8 to 20 carbon atoms or the group - (CH ₂ ) _m - COO ■ R ₆ , where R _{6 is} an alkyl radical having 4 to 30 carbon atoms and m is an integer from 1 to 4 -, for stabilization of already polymeric homo- or copolymers of alkylene oxides against degradation by heat and light. 609 503i416 1.66 © Bundcsdriickerci Berlin