DD147363A1 - METHOD FOR STABILIZING POLYOLEFINS AND OLEFIN COPOLYMERISES - Google Patents

Abstract

The invention relates to the stabilization of polyolefins and copolymers of olefins and vinyl-containing compounds against thermal and thermo-oxidative degradation. The life of the polymer products is increased by the action of the stabilizer during polymer processing and use. The stabilizer used is 1- (4-anilinophenyl) -1- (4'-N-hexenyl- (1) -anilinophenyl) -cyclohexane. The stabilizer is used in concentrations of 0.1 to 0.5% by weight, based on the polymer. The stabilizer is suitable for use alone or in combination with other additives such as e.g. Trinonylphenyl phosphite or dilaurylthidipropionate e.g. for the stabilization of polyethylenes, ethylene-vinyl acetate copolymer or mixtures of these two polymers.

Description

-A-

Title of the invention

Process for the stabilization of polyolefins and Olefineopolyreerisaten

Field of application of the invention

The invention relates to a process for the stabilization of polyolefins and copolymers of olefins and vinyl-containing compounds against thermal and thermo-oxidative degradation. , ,

Characteristic of the known technical solutions

The use of condensation products of ketones or aldehydes and amines, e.g. Example of acetone and diphenylamine (US-PS 2435245) or from cyclohexanone and diphenylamine (DD-PS 132498) to improve the stability behavior of polyolefin is known.

These diarylamine ketone condensation products have the disadvantage that, as liquid to resinous, more or less dark colored substance mixtures of unknown composition, they do not enter into the polymer satisfactorily in every pail under the customary technical incorporation conditions.

are workable or adversely affect the color of polymer finished parts.

Object of the invention

The aim of the invention is the use of a crystalline, colorless compound to improve the stabilization of polyolefins and copolymers «from olefins and vinyl-containing compounds against thermal and thermo-oxidative degradation

Explanation of the essence of the invention

The object of the invention is to use as stabilizer for polyolefins and copolymers of olefins and vinyl-containing compounds, an arylamine-ketone condensation product which is characterized by high purity, flowability, technically favorable incorporation without discoloration, compatibility and high activity in the polymer.

This object is achieved by a process for the stabilization of polyolefins, copolymers of olefins and vinyl-containing compounds and mixtures of both against thermal and thermooxidative degradation with a condensation product of diarylamine and ketone, erfindungsgernäß as stabilizer 1- (4-anilinophenyl) -1- ( 4 ^t -W-hexenyl- (1) -anilino-phenyl) -cyclohexane of the formula

Χ, - QC _r ii ~ ί · ί Li-G Λί

he π ^ c ^ °> ° 5

^N ^ C ^/ c ₆ H ₅ -NC ₆ H

C ₆ H ₉

The stabilizer is advantageously used in an amount of from 0.01% to 5% by weight, preferably from 0.1% by weight to 0.5% by weight, based on the formula Amount of polymer used. Advantageously, the stabilizer is used in amounts of 0.1 to 0.5% by weight and trinonylphenyl phosphite in amounts of 0 _? 05 to

0.5 Gevfm-% and / or a dilauryl thiodipropionate in amounts of 0.05 to 0.5 wt .-%, each based on the Polymerisatrnenge used. The stabilizer may additionally contain known aminic, phenolic, sulfur-containing or phosphorus-containing stabilizers, in particular organic phosphites, such as trinonylphenyl phosphite and triphenyl phosphite, and also organic sulfur compounds, such as dilauryl thiodipropionate, UV absorbers and other known additives,

The incorporation of the stabilizer in the polymer without or with further additives is advantageously carried out in the processing phase to the molding material in the usual processing conditions.

embodiments

example 1

0.2% by mass of 1 - (4-anilinophenyl) -1- (4'-l-hexenyl- (1) -anilinophenyl) -cyclohexane are mixed in high pressure polyethylene. The mixture is processed at 383 K within 10 minutes on a rolling mill to 0.2 mm thick films. The color stability of the film samples is tested at 423 K in air in a forced air oven. The following table shows the discoloration compared to the film sample without stabilizer and with known stabilizer.

Polyethylene color after h aging

0 12 24 36 48

without stabilizer, faintly pale yellow, yellowish-brown

go yellow

Polyethylene color after h aging

0 12 24 36 48

 with 1- (4-anilino ~

phenyl) -1 ~ (4 '"- ¥ - ~ color weak light" type light yellow hexenyl ~ (1) - S ^{los elb} yellow yellow

aniline · pheny 1) cyclohexane

with cyclohexanone collo- loa pale yellow light yellow light yellow yellow Diphenylamine condensate go crazy pale yellow yellow yellow yellow with di-tert-butyl p-cresol with 1- (4-anilinophenyl) - colorless go crazy go crazy colour- »go color go 1- (4'-H-hexenyl) - (1) -anilinophenyl) »cyclo- hexane and trinonylphenyl » phosphite

Example 2

0.2% by mass of 1 - (4-anilinophenyl) -1 - (4'-H-hexenyl- (1) -anilinophenyl) -cyclohexane are mixed in high-pressure polyethylene. The mixture is processed to 0 _s 2 mm thick films on the rolling mill at 383 K within 10 minutes. The film samples are then pressed into 0.03 mm thin films at 433 K within 2 minutes at 30 MPa. Dationostability of the film samples is tested at 443 K in pure oxygen. The following table shows the oxygen uptake of the film sample compared to the film sample without stabilizer and with known stabilizer. "

- 5 - 21 71 «5

Polyethylene start of oxygenation

take after minutes

without stabilizer 7

with 1- (4-anilinophenyl) -1- (4 ^! -N-hexenyl- (1) -anilinophenyl) -

cyclohexane 27

with cyclohexanone-diphenylamine

Condensate 14

with di-tert-butyl-p-cresol 9

with 1- (4-ailinophenyl) -1- (4 ^t -N-)

hexene: /! · »(1) ~ anilinophenyl) -cyclohexane and trinonylphenyl

phosphite 55

Example 3

0.2 percent by mass of 1- (4 ~ anilinophenyl) -1 ~ ^(4-f -Ii hexenyl (1) ~ anilinophenyl) ~ in ethylene-vinyl acetate copolymer (21% vinyl acetate by weight. ~) Cyclohexane are mixed. The mixture is processed at 313 K within 10 minutes on a rolling mill to 0.2 mm thick films. The color stability of the samples is tested at 423 K in air in a convection oven. Show the following table; the discoloration compared to the film sample without stabilizer and with known stabilizer.

fa ί

Ethylene copolymer Vlnylacetat

Color after h aging 0 12 24 36

color- weak yellow yellow · brown lo8 yellow brown color- color colored. weak weak Io β Come on Come on yellow yellow Lich Lich color weak yellow yellow yellow Come on yellow Lich Lich Lich Lich color- color yellow yellow brown Lich color- color color color color loa Come on Come on Come on Come on

without stabilizer '

with 1- (4-anilinophenyl) -1- (4 ^f -N-hexynyl- (1) -anilinophenyl) -cyclohexane with cyclohexanone-diphenylamine condensate

with di ~ tert ~ butyl-p-cresol _e

1 - (4-Anilinoplienyl) with ~ -1- (4 ~ ^f -N hexenyl (1) -anilinophenyl) cyclohexane

and trinonylphenylphosphite

Example 4

Oj2 mass percent of 1- (4 ~ anilinophenyl) ™ "1- (4 ^l ~ -K-hexenyl (1) -anilinophenyl) -cyclohexane be in ethylene-vinyl acetate copolymer (21 wt _e ~% vinyl acetate) blended" The mixture is processed 2 mm thick sheets at 313 K in 10 minutes on a rolling mill su O _S * the film samples ₅ 05 mm thin films are then at 353 K within 2 minutes at 30 MPa to O pressed * the oxidation stability of the film sample will be at 443 K The following table shows the oxygen uptake of the film sample compared to the film sample without stabilizer and with a known stabilizer.

Ethylene vinyl acetate copoly- Start of oxygenation after minutes

without stabilizer 7

with 1 '- (4-Anllino phenyl) - »1 -

(4 ^t ~ -N hexejayl- (1) ~ anilino-

PhenyD-cyclohexane 95

with cyclohexanone-diphenylamine

Condensate 15

with di-tert-butyl-p-cresol 12

with 1- (4-anilinophenyl) -1-

(4 ^f -U-hexenyl-1- (1) -anilinophenyl) -cyclohexane and

Trinonylphenyl phosphite 140

Example 5

Ο, 2 mass% 1 ~ (4 ~ anilinophenyl) -1- (4 ^! ~ N- »hexenyl ~ (1)" anilinophenyl) -cyclohexane be in a polymer mixture of high pressure polyethylene and ethylene-vinyl acetate copolymer in the ratio 95 to 5 The mixture is processed into 0.2 mm thick films on a rolling mill at 383 K. The color stability of the film samples is tested at 423 K in air in a circulating air oven «The following table shows the discoloration compared to the film sample without stabilizer and with known stabilizer *

ess J

Mixture of polyethylene and ethylene-vinyl acetate copolymer 0

Color after h aging

24 36

48

without stabilizer color weak yellow yellow brown Come on yellow brown with 1- (4-anilinophenyl) - 1- (4 ^T -N-hexenyl (1) -ani- color color bright yellow yellow linophenyl) -cyclohexane Come on Come on yellow with di-tert-butyl-p- color color bright yellow yellow cresol Come on Come on yellow brown

with 1- (4-anilinophenyl) -1- (4'-N-hexenyl- (1) -anilinophenyl) ~ cyclohexane and color trinonylphenyl phosphite

Example 6

colorless

colorless

colorless

light yellow

0.2% by weight of 1- (4-anilinophenyl) -1- (4'-N-hexenyl-d) -anilinophenyl) -cyclohexane in a polymer mixture of high-pressure polyethylene and ethylene-vinyl acetate copolymer in the ratio of 95 to 5 mass percent mixed »The mixture is processed at 383 K within 10 minutes on the rolling mill to 0.2 mm thick films. The film samples are then pressed at 433 K within 2 minutes at 30 MPa into 0.03 mm thin films. The oxidation stability of the film. Samples are tested at 443 K in pure oxygen. The following table shows the Sauerstoffaufnahme the film sample in comparison to the film sample without stabilizer and with known stabilizer.

Mixture of polyethylene and ethylene start of the oxygen-vinyl acetate Copolyinerisat recording to Minu

th

without stabilizer. 7

with 1- (4-anilinophenyl) -1- (4 ^f -lf-

hexenyl (1) -anilinophenyl) -Cyclo-

hexane 39

with cyclohexanone-diphenylamine

Condensate 22

with di-tert-butyl-p-cresol 8.

with ^< ! - (4-anilinophenyl) -1- (4'-N-

hexenyl (1) -anilinophenyl) -Cyclo-

hexane and trinonylphenyl phosphite 42

Claims (1)

Λ Γ \ invention claim 1". A process for the stabilization of polyolefins, copolymers of olefins and vinyl-containing compounds as well as mixtures of both against thermal and thermoozydativen degradation with a condensation product of diarylamine and ketone, characterized in that as a stabilizer 1- (4-anilino phenyl) -1- (4 ^f - li-hexenyl- (1) -anilinophenyl) -cyclohexane of the formula C "" ^V C ⁶ 5 '6 5 CC ^W 6 5. Ϊ 6 5 is used, optionally ' in combination with known stabilizers · 2β Process according to item 1, characterized in that the stabilizer in an amount of 0.01 to 5% by weight, preferably from 0.1 to 0.5% by weight, based on the amount of polymer, is used. 3 · Method according to item 1 and 2, characterized in that the stabilizer in amounts of 0.1 to 0.5% by weight and trinonylphenyl phosphite in amounts of 0.05 to 0.5% by weight and / or a Dilaurylthiodipropionat in quantities of 0.05 to 0.5 Gevj "- $, in each case based on the amount of polytnerisate used," 4 * Method according to item 1 and 3, characterized in that with the stabilizer additionally known amine, phenolic, sulfur-containing or phosphorus-containing stabilizers, in particular organic phosphites, such as trinonylphenyl phosphite and Triphenylphosph.it and organic sulfur compounds, such as Dilaurylthiodipropionat, UV absorbers and others known additives are used *