AT406583B

Stabilization of polyolefin composition in permanent contact with extracting media

Abstract

This record has no abstract on file.

AT406583B, drawing sheet 1 — Sheet 1 of 117

Term

Term ended

Expired 12 September 2016, 10 years ago.

12 claims: 1 independent, 11 dependent

1
Patentansprüche:Zusammensetzung, enthaltend a) ein Polyolefin, das im Dauerkontakt mit Wasser, chloriertem Trinkwasser, wässriger Salzlösung, verdünnten wässrigen Laugen oder C 2 -C 4 -Alkoholen steht, b) mindestens eine Verbindung aus der Gruppe der organischen Phosphite oder Phosphonite, mit der Bedingung, dass das Tris[2-tert-butyl-4-(2-methyl-4-hydroxy-5-tertbutylphenylthio)-5-methyl]-phenyl-phosphit ausgeschlossen ist, c) (i) mindestens eine Verbindung der Formel I oder II worin (Π) n die Zahl I oder 3 bedeutet, R, CrC^-Alkyl, C 5 -C 12 -Cycloalkyl, Phenyl oder C7-C 9 -Phenylalkyl darstellt, R 2 Wasserstoff, CrC^-Alkyl, C 5 -Ci 2 -Cycloalkyl, Phenyl oder Cr-Cg-Phenylalkyl bedeutet, R 3 Wasserstoff oder Methyl darstellt, wenn n 1 bedeutet, 9 r 6 R 4 Wasserstoff, Cj-C^Alkyl oder_CH 2 — P_c/ darstellt, ι Ο, R 7 I CH, wenn n 3 bedeutet, H 2 C' Ν γ° Y CH o R 5 Wasserstoff oder Methyl bedeutet, R 6 Wasserstoff, CrC^-Alkyl, unsubstituiertes oder durch Ct-C^Alkyl substituiertes AT 406 583 B M r+ Phenyl oder Naphthyl;oder-bedeutet, r R 7 Ci-C2o*Alkyl, unsubstituiertes oder durch C r C4-Alkyl substituiertes Phenyl oder Naphthyl darstellt, M r+ ein r-wertiges Metallkation ist, und r 1, 2 oder 3 bedeutet;oder (ii) mindestens eine Verbindung aus der Gruppe der sterisch gehinderten Amine mit einem Molekulargewicht das grösser als 500 ist und mindestens einen Rest der Formel III oder IV (IV) enthält, worin G Wasserstoff oder Methyl ist, G, und G 2 Wasserstoff, Methyl oder gemeinsam =0 bedeuten;oder (iii) (x) mindestens eine Verbindung aus der Gruppe der phenolischen Antioxidantien und (y) mindestens eine Verbindung aus der Gruppe der sterisch gehinderten Amine mit einem Molekulargewicht das grösser als 500 ist und mindestens einen Rest der Formel III oder IV enthält;mit der Bedingung, dass wenn die Komponente (a) Poly-1-buten und die Komponente (c)(i) 1,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol ist, die Komponente (b) nicht Tris(2,4-di-tert-butyl-phenyl)-phosphit bedeutet.
2
Zusammensetzung gemäss Anspruch 1, worin die Komponente (b) eine Verbindung der Formeln V, Ph-1, Ph-3 oder Ph-11 CiCHaJa C(CHa)3 (Ph-1) C(CHg)g CfCHala C(CHa) 3 (CHa) 3 C (Ph-3) AT 406 583 B H 3 C —c CI ch 3 CHg H 3 C-C —-O' P-o-CHg-CHg N (Ph-11) darstellt, worin Rg und Ri 2 unabhängig voneinander Wasserstoff, CrC 8 -Alkyl, Cyclohexyl oder Phenyl bedeuten, und R,o und Rn unabhängig voneinander Wasserstoff oder Ci-C 4 -Alkyl darstellen.
3
Zusammensetzung gemäss Anspruch 1, worin die Komponente (c)(i) eine Verbindung der Formel I oder II darstellt, worin n die Zahl 1 oder 3 bedeutet, Ri Ci-Ci2-Alkcyl, C 5 -C 8 -Cycloalkyl, Phenyl oder Benzyl darstellt, R 2 Wasserstoff, Ci-C 12 -Alkyl, C s -C 8 -Cycloalkyl, Phenyl oder Benzyl bedeutet, R 3 Wasserstoff oder Methyl darstellt, wenn n 1 bedeutet, o II R — ch 9 -p—o darstellt, wenn n 3 bedeutet, CH 3 AT 406 583 B 4. darstellt, R5 Wasserstoff oder Methyl bedeutet, M r+ R 6 Wasserstoff, Ci-C 12 -Alkyl oder-bedeutet, r R 7 Ci-Ci 2 -Alkyl darstellt, M r+ ein r-wertiges Metallkation ist, und r 1, 2 oder 3 bedeutet. Zusammensetzung gemäss Anspruch 1, worin die Komponente (c)(i) eine Verbindung der Formel I darstellt, worin n die Zahl 1 oder 3 bedeutet, Ri tert-Butyl, Cyclohexyl oder Phenyl darstellt, R 2 Wasserstoff, tert-Butyl, Cyclohexyl oder Phenyl bedeutet, R 3 Wasserstoff darstellt, wenn n 1 bedeutet, o R4 — CH 2 —R—O Re darstellt, °γγ° o darstellt, R6 C,-C 4 -Alkyl oder-bedeutet, 5. R 7 Ci-C 12 -Alkyl darstellt, M r+ Calcium ist, und r 2 bedeutet. Zusammensetzung gemäss Anspruch 1, worin die Komponente (c)(ii) oder die Komponente (c)(iii)(y) eine Verbindung aus der Gruppe der sterisch gehinderten Amine darstellt, worin das Molekulargewicht größer als 1000 ist und die Verbindung mindestens einen Rest der Formel VI oder VI 1 N / \ (VT) enthält, worin R 13 Wasserstoff oder Methyl bedeutet. AT 406 583 B
4
6. Zusammensetzung gemäss Anspruch 1, worin die Komponente (c)(ii) oder die Komponente (c)(iii)(y) eine Verbindung aus der Gruppe der sterisch gehinderten Amine darstellt, worin das Molekulargewicht größer als 1000 ist und die Verbindung mindestens einen Rest der Formel VI oder VI' und einen Rest der Formel VII (VI’) (ΥΠ) enthält, worin R 13 Wasserstoff oder Methyl bedeutet. 7. Zusammensetzung gemäss Anspruch 1, worin die Komponente (c)(iii)(x) eine Verbindung der Formel VII darstellt, worin R, CrC^-Alkyl, C 5 -C 12 -Cycloalkyl, Phenyl oder Cy-Cg-Phenylalkyl darstellt, R 2 Wasserstoff, C r Ci8-Alkyl, C s -C 12 -Cycloalkyl, Phenyl oder CrC 9 -Phenylalkyl bedeutet, R 3 Wasserstoff oder Methyl darstellt, —CH2—CH— QC m H 2lT , oder R 14 bedeutet, Ru Ci-C 8 -Alkyl darstellt, X Sauerstoff oder -NH- bedeutet, m die Zahl 0,1, 2 oder 3 darstellt, p die Zahl 1, 2 oder 4 bedeutet, und wenn p 1 ist, Ris C e -C 20 -Alkyl oder C 5 -C 12 -Cycloalkyl bedeutet, und wenn p 2 ist und X Sauerstoff darstellt, Ris C 2 -C 8 -Alkylen oder durch Sauerstoff oder Schwefel unterbrochenes C 4 -C 8 -Alkylen bedeutet;und wenn p 2 ist und X -NH- darstellt, AT 406 583 B R 15 eine direkte Bindung, C 2 -C 8 -Alkylen oder durch Sauerstoff oder Schwefel unterbrochenes C 4 -C 8 -Alkylen bedeutet, und wenn p 4 ist, R 15 C 4 -C 10 -Alkantetrayl darstellt.
5
8. Zusammensetzung gemäss Anspruch 7, worin die Komponente (c)(iii)(x) eine Verbindung der Formel I, n oder VIII darstellt, worin R-ι und R 2 tert-Butyl bedeutet, und m 2 darstellt.
6
9. Zusammensetzung gemäss Anspruch 1, worin die Komponente (c) die Komponente (i) oder die Komponente (iii) ist.
7
10. Zusammensetzung gemäss Anspruch 1, worin die Komponente (b) Tris(2 l 4-di-tert-butylphenyl)phosphit, Bis(2,4-di-tert-butyl-6-methyl)ethylphosphit oder eine Verbindung der Formel Ph-3 oder Ph-11 die Komponente (c)(i) eine Verbindung der Formel I, worin n 3 darstellt, Ri und R 2 tert-Butyl bedeuten, R 3 Wasserstoff ist und oder darstellt;die Komponenten (c)(ii) und (c)(iii)(y) lineare oder cyclische Kondensationsprodukte hergestellt aus N,N'-Bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylendiamin und 4-tertOctylamino-2,6-dichlor-1,3,5-triazin;oder ein Kondensationsprodukt hergestellt aus 2Chlor-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpipeddyl)-1,3,5-triazin und 1 ,2-Bis(3aminopropylamino)ethan bedeuten;und (CHgJgC die Komponente (c)(iit)(x) H 1 (OHa) 3 c AT 406 583 B (CH^C Hi CHä) 3 C Hi o II oder CHj - CH 2 — C-O — n-C 18 H 37 darstellt. (CH^C
8
11. Zusammensetzung gemäss Anspruch 1, enthaltend neben den Komponenten (b) und (c) zusätzlich weitere Additive, insbesondere Antioxidantien.
9
12. Zusammensetzung gemäss Anspruch 1, enthaltend als Komponente (a) Polyethylen oder Polypropylen und deren Copolymere mit Mono- und Diolefinen.
10
13. Zusammensetzung gemäss Anspruch 1, worin die Komponente (b) in einer Menge von 0,02 bis 0,6 % und die Komponente (c) in einer Menge von 0,02 bis 1,0 % bezogen auf das Gewicht der Komponente (a) vorliegt.
11
14. Zusammensetzung gemäss Anspruch 1, worin die Komponente (c)(iii)(x) in einer Menge von 0,02 bis 0,5 % und die Komponente (c)(iii)(y) in einer Menge von 0,02 bis 1,0 % bezogen auf das Gewicht der Komponente (a) voriiegt.
12
15. Verwendung einer Mischung enthaltend eine Komponente (b) und eine Komponente (c) gemäss Anspruch 1 zum Stabilisieren von dickschichtigen Polyolefinformkörpem, die im Dauerkontakt mit Wasser, chloriertem Trinkwasser, wässriger Salzlösung, verdünnten wässrigen Laugen oder Ci-C 4 -Alkoholen sind.

Independent claims12

1,029 paragraphs in 74 sections, as filed

The present invention relates to compositions containing a polyolefin which, in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkaline solutions or C.1-C4-Alcohols stands and stabilizer mixtures, the use of the same for stabilizing thick-layered polyolefin moldings and a method for stabilizing thick-layered polyolefin moldings.

From R. Gächter and H. Müller, Plastics Additives Handbook, 3rd Edition, pages 1 to 100 (1990), it is known, for example, that polyolefins can be protected against oxidative damage during production, processing and use by suitable stabilizer mixtures. In many cases, the stabilized polyolefin moldings are in contact with liquid or gaseous media during use. It is therefore necessary that the stabilizer mixtures added to the polyolefin molding have sufficient chemical resistance to the respective contact media. Polyolefin moldings that are particularly at risk are, for example, pipes, submarine cables, tanks or geomembrane that are in constant contact with extracting media.

EP-A-0 324 106 describes a polyolefin molding compound which has particularly good stability when in constant contact with extracting media. A symmetrical triaryl phosphite and an ester of 3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butanoic acid are used as the stabilizer mixture.

US-A-4,532,165 discloses a resin composition containing a poly-1-butene and at least one hindered phenol selected from eleven different groups of phenolic antioxidants. These resin compositions are said to have excellent resistance to hot or cold water containing chlorine.

Japan Patent Kokai Hei 1-103638 discloses a polyolefin composition having an improved resistance to chlorinated and unchlorinated water in a temperature range of 0 ° to 100 ° C, containing a) 93-99.5% by weight of an isotactic polymer of an α-olefin with 3-6 carbon atoms, b) 0.05-0.50% by weight of a hindered amine UV stabilizer; c) 0.05-1.1% by weight of a sterically hindered phenolic heat stabilizer with a molecular weight of at least 530 and selected from the group consisting of 1,3,5-trimethyl-2,4,6-tris (3,5- di-tert-butyl-4-hydroxy-benzyl) -benzene, octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate, tetrakis [methylene- (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) ]-methane, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, bis [ 3,3-bis (4'-hydroxy-3'-tert-butyl-phenyl) -butyric acid] -glycol ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and mixtures thereof; d) 0-0.5% by weight of a nucleating agent; e) 0-4% by weight of a pigment; f) 0-3.0% by weight of a filler; and g) 0.1-3.0% by weight of a complexing agent selected from the group consisting of 2,2'-oxamidobis- [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) - propionate], N ', N'-bis [3- (3,5-di-tert-butyl4-hydroxyphenyl) -propanylhydrazine, calcium bis [monoethyl (3,5-di-tert-butyl ~ 4-hydroxybenzyl)] phosphonate and tris [2-tert-butyl-4- (2-methyl-4-hydroxy-5-tert-butylphenylthio) -5-methyll-phenyl phosphite.

It has now been found that a selected mixture containing an organic phosphite or phosphonite and a specially selected group of sterically hindered phenols or a certain group of sterically hindered amines are particularly suitable as stabilizers for polyolefin moldings which are in constant contact with water, chlorinated drinking water, aqueous saline solution, dilute aqueous alkaline solutions or CiC4-Alcohols are available. It has also been found that a mixture of three containing a phosphite or phosphonite, a phenolic antioxidant and a certain group of sterically hindered amines are particularly suitable as stabilizers for polyolefin moldings which are in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkalis or Ci -C4Alcohols.

The present invention therefore relates to compositions containing

a) a polyolefin that is in constant contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkalis or Ci-C ^ alcohols,

b) at least one compound from the group of organic phosphites or phosphonites, with the condition that the tris [2-tert-butyl-4- (2-methyl-4-hydroxy-5-tert-butylphenylthio) -5methylj-phenyl- phosphite is excluded,

c) (i) at least one compound of the formula I or II

AT 406 583 B (II)

where n is the number 1 or 3,

Ri Ci-C18-Alkyl, C5-C12-Cycloalkyl, phenyl or Cy-Cg-phenylalkyl,

R.2 Hydrogen, Ci-Ci8-Alkyl, Cs-Ci2-Cycloalkyl, phenyl or CrCg-phenylalkyl, R3 When n is 1, represents hydrogen or methyl, O

II /R.*

R.4 Hydrogen, CrC.4-Alkyl or ~ CH2 P. 0 represents

R.7 if n means 3,

I2

Υύ °

Λ 'νΥν ο

CHs

CH3- CH - CH2, - represents CH,

I \

R.5 Is hydrogen or methyl, R6 Hydrogen, C 1 -C 10 -alkyl, unsubstituted or substituted by C.r M.r +

C.4-Alkyl substituted phenyl or naphthyl; or-means r

R.7 CrCarAlkyl, unsubstituted or by C1-C4-Alkyl-substituted phenyl or naphthyl,

M.f + is an r-valent metal cation and r is 1, 2 or 3; or (ii) at least one compound from the group of sterically hindered amines having a molecular weight greater than 500 and at least one radical of the formula in or IV

contains where

G is hydrogen or methyl,

G1 and G2 Denotes hydrogen, methyl or together = 0; or (iii) (x) at least one compound from the group of phenolic antioxidants and (y) at least one compound from the group of sterically hindered amines with a molecular weight greater than 500 and containing at least one radical of the formula III or IV; with the condition that if the

AT 406 583 B

Component (a) is poly-1-butene and component (c) (i) is 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, component (b) is not tris (2,4-di-tert-butyl-phenyl) phosphite.

Alkyl with up to 20 carbon atoms means a branched or unbranched radical such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methyl-heptyl, n-octyl, 2-ethylhexyl, 1,1, 3Trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl. A preferred meaning of R-ι and R2 is Ci-C ^ -alkyl, in particular 0, Ce-alkyl, for example tert-butyl. A particularly preferred meaning of R7 is CrC.12-Alkyl, especially CrCi0-Alkyl, for example Ci-C8-Alkyl.

C.5-C,2-Cycloalkyl, especially C5-C8-Cycloalkyl means, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclohexyl is preferred.

CrCg-Phenylalkyl means, for example, benzyl, a-methylbenzyl, aa-dimethylbenzyl or 2-phenylethyl.

By Ci-C4-Alkyl-substituted phenyl or naphthyl, which preferably contains 1 to 3, in particular 1 or 2, alkyl groups means, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5- Dimethylphenyl, 2,6-dimethylphenyl, 3,4dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl or 4-tert-butylnaphthyl.

A one-, two- or three-way metal cation is preferably an alkali metal, alkaline earth metal, heavy metal or aluminum cation, for example Na+ K *. Mg **, Ca **, Ba **, Zn ** or AI ***. Ca ** is particularly preferred.

Of interest are compositions containing, as component (b), organic phosphites or phosphonites of the formulas (1) to (7),

O— </ —O R.',“OP.\ _Ä_?-O'R.'’ (5) o— '\ —O

AT 406 583 Β

where the indices are integers and n 'is 2, 3 or 4; p for 1 or 2; q for 2 or 3; r for 4 to 12; y is 1, 2 or 3; and z is 1 to 6;

A 'when n' is 2 is alkylene of 2 to 18 carbon atoms; by -S-, -O- or -NR '4interrupted alkylene of 2 to 12 carbon atoms; a remainder of one of the formulas

Is phenylene;

A 'when n' is 3 is a radical of the formula -CrH2r-i-is;

A ', when n' is 4, is the remainder of the formula C (CH2)4- means;

A has the meaning of A 'when n' is 2;

B 'is a radical of the formula -CH2-; -CHR '4-; -CR ', R'4-; -S- or a direct bond; or C5Cr-cycloalkylidene; or with 1 to 4 C, -C4-Alkyl radicals in position 3,4 and / or 5 is substituted cyclohexylidene;

D 'when p is 1 is methyl and when p is 2 -CH2OCH2- means;

E 'when y is 1 is alkyl of 1 to 18 carbon atoms, a radical of the formula -OR'i or halogen;

E 'when y is 2 is a radical of the formula -OAO-;

E ', if y is 3, a radical of the formula R'4C (CH2Ö) 3— is;

Q 'stands for the radical of an at least z-valent alcohol or phenol, this being bonded to the P atom (s) via the alcoholic or phenolic O atom (s) is;

R'i, R 'z and R '3 independently of one another alkyl having 1 to 30 carbon atoms; with halogen, COOR4', -CN or -CONR4'R4'substituted alkyl of 1 to 18 carbon atoms; by -S-, -O or -NR '4- interrupted alkyl of 2 to 18 carbon atoms;

Phenyl-CvC 1-4 alkyl; Cycloalkyl of 5 to 12 carbon atoms; Phenyl or naphthyl;

phenyl or naphthyl substituted with halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms or phenyl-C 1 -C 4 alkyl; or a residue of the formula

are, where m is an integer from the range 3 to 6

R '4 or the radicals R / independently of one another are hydrogen; Alkyl of 1 to 18 carbon atoms; Cycloalkyl of 5 to 12 carbon atoms; or phenylalkyl with 1 to 4 carbon atoms in the alkyl part;

R's and R '6 independently of one another hydrogen; Are alkyl of 1 to 8 carbon atoms or cycloalkyl of 5 or 6 carbon atoms;

AT 406 583 B

R '7 and R'a, in the case q - 2, independently of one another represent CvC ^ alkyl or together represent a 2,3-dehydropentamethylene radical; and R '7 and R '8, in the case q = 3, are methyl; the substituents R '14 independently of one another hydrogen; Are alkyl of 1 to 9 carbon atoms or cyclohexyl;

the substituents R '15 independently of one another hydrogen or methyl; and R '56 Hydrogen or C.1-C4-Alkyl and in the case that several radicals R '16 are present, the residues R '16 are the same or different;

X 'and Y * each represent a direct bond or -O-, · and Z' a direct bond; -CH2-; C (R'i6) is 2- or -S-.

Of particular interest are compositions containing as component (b) a phosphite or phosphonite of the formula (1), (2), (5) or (6), in which n 'for the number 2 and y for the number 1 or 2 stands;

A 'alkylene of 2 to 18 carbon atoms; is p-phenylene or p-biphenylene;

E 'in the case y = 1 Ci-Cie-Alkyl, -OR, or fluorine; and in the case y = 2 p-biphenylene;

R'i, R '2 and R '3 independently of one another alkyl having 1 to 18 carbon atoms;

Phenyl-C, -C4-alkyl; Cyclohexyl; Phenyl; denotes phenyl substituted by 1 to 3 alkyl radicals with a total of 1 to 18 carbon atoms;

the substituents R '14 are independently hydrogen or alkyl having 1 to 9 carbon atoms;

R '15 Is hydrogen or methyl;

X 'is a direct bond;

Y1 -O-; and Z is a direct bond or -CH (R '16)- is.

Also of interest are compositions containing, as component (b), phosphites or phosphonites of the formula (1), (2), (5) or (6), in which n 'stands for the number 2 and y for the number 1;

A 'is p-biphenylene;

E 'is QC-ie-alkoxy or fluoro;

R '· ,, R'2 and R '3 independently of one another alkyl having 1 to 18 carbon atoms; is phenyl substituted by 2 or 3 alkyl radicals with a total of 2 to 12 carbon atoms; the substituents R'i4 are independently methyl or tert-butyl;

R '15 Is hydrogen;

X 'is a direct bond;

Y'-O-; and Z 'a direct bond, -CH2- or -CH (CH3)- is.

Compositions containing, as component (b), phosphites, in particular those of the formulas (1) and (5), are particularly preferred.

The following compounds are examples of phosphites and phosphonites which are particularly suitable as component (b) in the composition according to the invention.

C (CH3) 3 (Ph-1);

(Ph-2);

AT 406 583 B

C (CH3)3

(CHgJgC

AT 406 583 B

(Ph-8);

(Ph-9);

O-κ r-Q

H37C.18-Op'Y VOC ^ o-f> -Q (Ph-10);

(Ph-11).

AT 406 583 B

The phosphites and phosphonites mentioned are known compounds; some of them are commercially available.

Compositions containing as component (b) a compound of the formulas V, Ph-1, Ph-3 or Ph-11 are particularly preferred

C (CH3)3 (Ph-1)

C (CH3)3

C (CH3) 3 (Ph-3) (CH3)3C.

• —o — ch2—Ch2N (Ph-11)

AT 406 583 B wherein

R.9 and R12 independently of one another are hydrogen, C 1 -C 5 -alkyl, cyclohexyl or phenyl, and

R.10 and Rn independently of one another hydrogen or CrC.4Represent -alkyl.

Compositions of interest are those containing, as component (c) (i), a compound of the formula I or II, in which n is the number 1 or 3,

Ri CrCu-alkyl, C5-C8-Cycloalkyl, phenyl or benzyl,

R.2 Hydrogen, CrC12-Alkyl, C5-C8-Cycloalkyl, phenyl or benzyl,

R.3 Represents hydrogen or methyl, if n is 1,

R.4

Rs represents

CH2 >z Y «K o

or /

CH3Represents -CH — CHa-CH,

R.5 Means hydrogen or methyl,

M.r +

R.6 Hydrogen, CrCi2-alkyl or-means,

R.7 CrC12Represents -alkyl,

M.r + is an r-valent metal cation, and r is 1, 2 or 3

Preferred compositions are those containing, as component (c) (i), a compound of the formula I in which n is the number 1 or 3,

R represents tert-butyl, cyclohexyl or phenyl,

R.2 Is hydrogen, tert-butyl, cyclohexyl or phenyl,

R.3 Represents hydrogen when n is 1, o

II z *6 CH2-P —o

represents when n is 3,

AT 406 583 B

CHg

Ϋϊ ° ο

M.r +

Re Ci-C4-Alkyl or-means, r

R.7 Represents CrC ^ -alkyl,

M.r + Is calcium, and r is 2

Very particularly preferred are compositions which represent compounds of the formula containing as component (c) (i),

OH

Irganox® 1330 (Ciba-Geigy)

OH

Irganox® 3114 (Ciba-Geigy)

AT 406 583 B

O

II l2-P — OCHsCHa OCHgCHa

Irganox® 1222 (Ciba-Geigy)

Irganox® 1425 (Ciba-Geigy)

Of particular interest are compositions containing as component (c) (ii) or as component (c) (iii) (y), sterically hindered amines of the under (a1) to (g1) described class of compounds which contain at least one radical of the formula in or IV.

(a1) Compounds of the formula IV r gch2 ch3 q1q1-n \ - v__f gch2/ xch3

-G n

dV ') where n is a number from 1 to 4, G and G1 are independently hydrogen or methyl,

G11 Hydrogen, oxyl, hydroxyl, C, -Ci8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C7-Ci2-aralkyl, CrCi8alkoxy, C5-C8-cycloalkoxy, Cy-Cg-phenylalkoxy, CrCe-alkanoyl, C3 -C5-alkenoyl, Ci-C18alkanoyloxy, benzyloxy, glycidyl or a group -CH2CH (OH) -Z, in which Z is hydrogen, methyl or phenyl, where G11 is preferably H, C 1-4 alkyl, allyl, benzyl, acetyl or acryloyl and G12when n is 1, hydrogen, optionally interrupted by one or more oxygen atoms Ci-Ci8-alkyl, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monobasic acid Silyl radical, preferably a radical of an aliphatic carboxylic acid with 2 to 18 carbon atoms, a cycloaliphatic carboxylic acid with 7 to 15 carbon atoms, an α, β-unsaturated carboxylic acid with 3 to 5 carbon atoms or an aromatic carboxylic acid with 7 to 15 carbon atoms, the carboxylic acid in each case in the aliphatic, cycloaliphatic or aromatic part with 1 to 3

AT 406 583 B

Groups -COOZ12 may be substituted, wherein Z12 H, C 1 -C 4 alkyl, C3-C12-Alkenyl, C5-C7cycloalkyl, phenyl or benzyl, when n is 2, is C2-Ci2-Alkylene, C4-Ci2-Alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, Dl-carbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid with 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid Means 8-14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8-14 carbon atoms, wherein the dicarboxylic acid in each case in the aliphatic, cycloaliphatic or aromatic part with 1 or 2 groups -COOZ12 can be substituted, if n is 3, a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which in the aliphatic, cycloaliphatic or aromatic part with -COOZ12 may be substituted, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical and, when n is 4, denotes a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Among the specified carboxylic acid residues are in each case residues of the formula (-CO)nTo understand R, where the meaning of n is given above, and the meaning of R results from the given definition.

Any substituents Ci-Ci mean2-Alkyl, so they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n -Un-decyl or nDodecyl.

In the meaning of Ci-C18-Alkyl can be G.11 or G12 for example represent the groups listed above and additionally, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If G11 C.3-C8If -Alkenyl is, it can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 4-tert-butyl-2-butenyl.

Gi1 is as C3-C8-Alkynyl preferably propargyl. As Cy-C ^ -aralkyl, G11 especially phenethyl and especially benzyl.

G11 is as CrCe-alkanoyl, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C3-C5-Alkenoyl, especially acryloyl.

Does Gf2 a monovalent radical of a carboxylic acid, it is, for example, an acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid radical .

Does G12 a monovalent silyl radical, it represents, for example, a radical of the formula (CjH ^ -SKZ '^ Z, where j is an integer from the range from 2 to 5, and Z' and Z 'independently of one another Ci-C4-Alkyl or CrC.4-Alkoxy mean.

Does G12 a divalent radical of a dicarboxylic acid, it represents, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid -, butyl (3,5di-tert-butyl-4-hydroxybenzyl) malonic acid or bicycloheptenedicarboxylic acid radical.

Provides G12 If a trivalent radical of a tricarboxylic acid is, it means, for example, a trimellitic acid, citric acid or nitrilotriacetic acid radical.

Provides G12 represents a tetravalent radical of a tetracarboxylic acid, it means, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

Does G12 a divalent residue of a dicarbamic acid, it represents, for example, a hexamethylene dicarbamic acid or a 2,4-toluene-dicarbamic acid residue.

Preference is given to compounds of the formula IV in which G is hydrogen, G11 Is hydrogen or methyl, n is 2, and G12 is the diacyl radical of an aliphatic dicarboxylic acid with 4-12 carbon atoms.

Examples of polyalkylpiperidine compounds of this class are the following compounds:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine

2) 1 -Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

3) 1 -Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine

5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine

6) 1-Ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine

7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine

8) 1,2,2,6,6-Pentamethylpiperidin-4-yl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate

9) Di- (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) -maleate

10) Di- (2,2,6,6-tetramethylpiperidin-4-yl) succinate

11) Di- (2,2,6,6-tetramethylpiperidin-4-yl) -glutarate

AT 406 583 B

12) Di- (2,2,6,6-tetramethylpiperidin-4-yl) adipate

13) Di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate

14) Di- (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate

15) Di- (1,2,3,6-tetramethyl-2,6-diethyI-piperidin-4-yl) sebacate

16) Di (1 -allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

17) 1-Hydroxy-4-β-cyanoethyloxy-2,2,6,6-tetramethylpiperidine

18) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl-acetate

19) Trimellitic acid tri- (2,2,6,6-tetramethylpiperidin-4-yl) ester

20) 1-Acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine

21) Diethylmalonic acid di (2,2,6,6-tetramethylpiperidin-4-yl) ester

22) Dibutyl malonic acid di (1,2,2,6,6-pentamethylpiperidin-4-yl) ester

23) Butyl (3,5-di-tert-butyl-4-hydroxybenzyl) -malonic acid-di- (1,2,2,6,6-pentamethyl-piperidin-4-yl) -ester

24) Di (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

25) Di (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

26) hexane-Γ, 6'-bis- (4-carbamoyloxy- 1-n-butyl-2,2,6,6-tetramethyl-piperidine)

27) toluene-2 ', 4'-bis- (4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethyl-piperidine)

28) Dimethyl-bis (2,2,6,6-tetramethylpipendin ~ 4-oxy) -silane

29) Phenyl-tris- (2,2,6,6-tetramethylpiperidin-4-oxy) -silane

30) tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite

31) Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate

32) Phenyl [bis (1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate

33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine

34) 4-Hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine

35) 4-Hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine

36) 1-Glycidyl-4-hydroxy-2,2,6,6-tetramethylpipendin (b ') compounds of the formula V G1S

Γ GChU gch /

CHs ft 1

q «(V ') where n is the number 1 or 2, G, G1 and G11 have the meaning given under (a '), G13 Hydrogen, CrC.12-Alkyl, C2-C5-Hydroxyalkyl, C5-C7-cycloalkyl, CrC.8-Aralkyi, C.2-C18-Alkanoyl, C.3-C5-Alkenoyl, benzoyl or a group of the formula

is and

G14when n is 1, hydrogen, Ci-Ci8-Alkyl, C3-C8-Alkenyl, C.5-C7-Cycloalkyl, CrCMlkyl, Glycidyi substituted with a hydroxy, cyano, alkoxycarbonyi or carbamide group, a group of the formula -CH2-CH (OH) -Z or of the formula -CONH-Z where Z is hydrogen, methyl or phenyl becfeut ^ t * when n is 2, C2-Ci2-Alkylene, C6-C12-Arylene, xylylene, a -CH2-CH (OH) -CH2-Group or a group -CH2-CH (OH) -CH2-ODO- means where DC2-C10-Alkylene, C6-C15-Arylene, C.6-C12Is cycloalkylene, or provided that G13 not alkanoyl, alkenoyl or benzoyl, G also means 1-oxo-C2-C12-alkylene, a divalent radical of an aliphatic, cycloaliphatic or

AT 406 583 B aromatic dicarboxylic acid or dicarbamic acid or the group -CO-, or, if n is 1, G13 and G14 together can mean the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Place any substituents C, -Ci2- or C, -C18-Alkyl, they have the meaning already given under (a ').

If any substituents are C5-C7-cycloalkyl, they are in particular cyclohexyl.

As C7-C8-Aralkyl is G.13 especially phenylethyl or especially benzyl. As C2-C5Hydroxyalkyl is G.13 in particular 2-hydroxyethyl or 2-hydroxypropyl.

G13 is as C2-Ci8-Alkanoyl, for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as C.3-C5-Alkenoyl, especially acryloyl.

Does G14 C.2-C8-Alkenyl, then it is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

G14 than C 1 -C 6 substituted with a hydroxy, cyano, alkoxycarbonyl or carbamide group4Alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) -ethyl.

Make any substituents C2-C12-Alkylene is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Any substituents are C6-C15-Aryls, they represent, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

As C6-C,2-Cycloalkylene should be mentioned in particular cyclohexylene.

Preferred compounds of the formula V are those in which n is 1 or 2, G is hydrogen, G11 Is hydrogen or methyl, G.T3 Hydrogen, CrC.12-Alkyl or a group of the formula

is and G14 in the case of n = 1 hydrogen or C, -C12-Alkyl, and in the case of n = 2 C2-C8-Alkylene or 1-oxo-C2-C8-alkylene is.

Examples of polyalkylpiperidine compounds of this class are the following compounds:

37) N, N '-Bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6-diamine

38) N, N '-Bis- (2,2,6,6-tetramethylpiperidin-4-yl) -hexamethylene-1,6-di-acetamide

39) bis (2,2,6,6-tetramethylpiperidin-4-yl) amine

40) 4-Benzoylamino-2,2,6,6-tetramethylpiperidine

41) N, N '-Bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N, N' -dibutyl-adipamide

42) N, N '-Bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N, N' -dicyclohexyl-2-hydroxypropylene-1,3-diamine

43) N, N '-Bis- (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylene-diamine

44) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) succinic diamide

45) N- (212,6,6-Tetramethylpiperidin-4-yl) -β-aminodipropionic acid di- (2,2,6,6-tetramethylpiperidin-4-yl) ester

46) The compound of the formula

AT 406 583 B

47) 4- (bis-2-hydroxyethyl-amino) -1,2,2,6,6-pentamethylpiperidine

48) 4- (3-Methyl-4-hydroxy-5-tert-butyl-benzoic acid amido) -2,2,6,6-tetra-methylpiperidine

49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidm (c ') compounds of the formula VI gch ^ cHq' ö,-Ö <

GCHj ^ CHj ° (VT) where n is the number 1 or 2, G, G1 and G11 have the meaning given under (a) and G15when n is 1, C2-C8-Alkylene or -hydroxyalkylene or C4-C22-Acyloxy-alkylene, when n is 2, the group (-CH2)2C (CH2-)2 means.

Does G1ff C.2-C8-Alkylene or -hydroxyalkylene, it represents, for example, ethylene, 1-methylethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene.

As C4-C22-Acyloxyalkylene means G.15 for example 2-ethyl-2-acetoxymethylpropylene. Examples of polyalkylpiperidine compounds of this class are the following compounds:

50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro [ 5.5] undecane

52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane

53) 9-Aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] undecane

54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane

55) 2,2,6,6-tetramethylpiperidine ^ -spiro-2 '- (1,,3'T-dioxall) -5'-spiro-5- (1,3-dioxane) -2-spiro-4 '(2', 2,, 6 ', 6'-tetramethylpiperidine);

(d ') Compounds of the formulas VIIA, VIIB and VIIC, compounds of the formula VIIC being preferred, r gch2

GCHj / iC 16 CH3G | , N-C = O

CH

C - N3 n

N - C = O i

H> 17 (VIIA) (VHB)

AT 406 583 B

o-c-τ.

(VHC) where n is the number 1 or 2, G, G1 and G11 have the meaning given under (a '),

G16 Is hydrogen, CrCirAlkyl, allyl, benzyl, glycidyl or C2-C6-alkoxyalkyl and G17when η is I, hydrogen, Ci-C12-alkyl, C3-Cs-Alkenyl, Cz-Cg-aralkyl, Cs-Cy-cycloalkyl, C2-C4-hydroxyalkyl, C2-C6-ACoxyalkyl, C.6-Ci0-Aryl, glycidyl or a group of the formula - (CH2)P.-COO-Q or the formula - (CH2)P.-O-CO-Q is where p is 1 or 2 and Q is Ci-C4-Alkyl or phenyl when n is 2 are C2Ci2-Alkylene, C4-C12-Alkenylene, C6-C12-Arylene, a group -CH2-CH (OH) -CH2-OH YES2-CH (OH) CH2- where DC2-C10-Alkylene, C6-C15-Arylene, C.s-C12-Cycloalkylene, or a group CH2CH (OZ ') CH2- (OCH2-CH (OZ ') CH2)2- means where Z 'is hydrogen, Ci-C,8-Alkyl, allyl, benzyl, C2-Ci2-Alkanoyl or benzoyl, and T2 independently of one another hydrogen, C, -C18-Alkyl or optionally by halogen or CrC.4-Alkyl substituted C6-Ci0-Aryl or C7-C9-Aralkyl or Tt and T mean2 together with the C atom that binds them, a C5-C14-Cycloalkane ring form.

If any substituents are CrC ^ -alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n- Decyl, n-undecyl or n-dodecyl.

Any substituents in the meaning of Ci-C18-Alkyl can represent, for example, the groups listed above and also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any substituents are C2-C6-Alkoxyalkyl, they represent, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

Provides G17 C.3-C5-Alkenyl, it means, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

As CrCg-aralkyl, G17, Ti and T2 especially phenethyl or especially benzyl. Form T, and T2 together with the carbon atom a cycloalkane ring, this can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

Does G17 C.2-C4-Hydroxyalkyl, it represents, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C6-C10-Aryl mean G17, T, and T2 in particular phenyl, a- or ß-naphthyl, optionally with halogen or Ci-C4-Alkyl are substituted.

Provides G17 C.2-Ci2-Alkylene is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

As C4-Ci2-Alkenylene means G17 in particular 2-butenylene, 2-pentenylene or 3-hexenylene.

Does G17 C.6-C12-Aryien, it represents, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Means Z 'C2-Ci2-Alkcanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

D has as C2-C10-Alkylene, C6-C15-Arvlen or C6-C12-Cycloalkylene has the meaning given under (b ').

Examples of polyalkylpiperidine compounds of this class are the following compounds:

56) 3-Benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione

57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione

58) 3-Allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro [4.5] decane-2,4-dione

59) 3-Glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro [4.5] decane-2,4-dione

60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione

61) 2-iso-propyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane

62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4.5] decane

63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro [5.1.11.2] -heneicosane

64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-spiro- [4.5] decane and preferably:

65) 8-Acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5] -decane-2,4-dione

AT 406 583 B

65) 8-Acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4.5] -decane-2,4-dione or the compounds of the following formulas:

AT 406 583 B (e ') compounds of the formula VIII', which in turn are preferred,

n (vm ') where n is the number 1 or 2 and G18 a group of one of the formulas

G1

CH, 'CH - E - (A) - CH \ _ ^ CH2GN-G11 or

CH, CH2G

G2 θ C.| ^ CH2G E- (A> —NN —G11λ—A ch, ch2g means where G and G11 have the meaning given under (a ') and G1 and G2 Hydrogen, methyl or together a substituent = 0, E denotes -O- or -NG13- is, A C2-C6-Alkylene or - (CH2)3-O- and x are one of the numbers 0 or 1,

G13 Represents hydrogen, Ci-Cu-alkyl, C2-C5-hydroxyalkyl or C5-C7-cycloalkyl, G19 equal to G18 or one of the groups -NG2 Ό22, -OG23, -NHCH2G23 or -N (CH2OG23) 2 is

G20when n = 1, equals G18 or G, and when n = 2, is a group -EBE-, in which B is C2-C8-alkylene or by 1 or 2 groups -N (G21) - interrupted C2-C8-Alkylene means

G21 C ^ Cu alkyl, cyclohexyl, benzyl or CrC4-Hydroxyalkyl or a group of the formula

is G22 CrC 1-4 alkyl, cyclohexyl, benzyl, Ci-C4-Hydroxyalkyl and G.23 Hydrogen,

Ci-Ci2-Alkyl or phenyl or G21 and G22 together C4-C5-Alkylene or -oxaalkylene, for example e'iVy · - v /, or G21 a group of the formula or a group of the formula

-CFfeCHa \ -G11

-CHzCHg7

AT 406 583 B

Any substituents Ci-Ci mean2-Alkyl, they represent, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

If any substituents are Ci-C4-hydroxyalkyl, they represent, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Means AC2-C6-Alkylene, for example, ethylene, propylene, 2,2-dimethyl-propylene, tetramethylene or hexamethylene.

Make G21 and G22 together C4-C5-Alkylene or oxaalkylene, this means, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds of this class are the compounds of the following formulas:

AT 406 583 B

76)

R-NH- (CH2) 3-A- (CH2) 24J- <CH2) 3-NH-R (amine J)

AT 406 583 B with R =

77)

CH3 rr CH3

RN- (CH2)3-OH2)2-N- (CH2) 3-NR with R =

78)

AT 406 583 B

(f) Oligomeric or polymeric compounds whose repeating structural unit contains a 2,2,6,6-tetraalkylpiperidine radical, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and their copolymers which contain such radicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds of this class are the compounds of the following formulas, where m is a number from 2 to about 200

81)

CH3 ch3 .

O 0 VL

II ii / \

C-CH2-CH2-CO-CH2-CH2-N Vo

CH,

82) CH3k CH3 O q CH3 CH3 ο O-,

Y- \ ii h II

-CHa-CHjj -N YOC- (CH2L-C-0-6 N-CH2-CHj> -OC • - (CHj>) 4-C - ch3 ch3 ch7ch3

-in the

AT 406 583 B

83)

84)

85)

86)

87)

CH.

CH3 .C.2H5 O

QNH4

VCH3 CzHg

N · chZnh\H,

-CH2-CH (OH> -CH2-l · J m

AT 406 583 B

89)

90)

91)

AT 406 583 B

92)

N - (CH2> 6-N - CHa-CHa—}

93) H3C. , CH3 H3C. 7 H.

CHg 'CH,

94)

-fN - {CHaJe-N · ^ /> ch3 rS.

ch3 ff CH3 ch3^'x

O

C-CHa

“N '

H ch3

CH,

95)

Γ RR

- ^ - NHCHaia-N-iCHaJa '^ m' where R =

is or for

Η a branch of the chain - (CH ^ -nJ - stands, m 'and m each an integer from the range m

AT 406 583 B

0-200 means with the condition m '+ m = m.

Further examples of polymeric compounds are reaction products of compounds of the formula

with epichlorohydrin; Polyester from butane-1,2,3,4-tetracarboxylic acid with a bifunctional alcohol of the formula

HO

CH

O — CH, CH, —O CK, OH i / \ / \ i / c — CH C CH — C — CH,

IV / I o-ch2 ch2-O

CH, whose carboxyl side chains derived from the tetracarboxylic acid are esterified with 2,2,6,6-tetra-methyl-4hydroxypiperidine; Compounds of the formula

CK »; h2- c-ch o = c OCH,

CH 'IO = C i

OR H3cX / ch3 where about one third of the radicals R is -C2H5 and the other - (Vl - H hJ / 'cHs mean and m is a number from the range from 2 to 200; or Copoiymerisate whose J- \ CH3

Recurring unit from 2 units ff \ —0 = 0¾ and 1 unit each

0=^3=0

is constructed.

(g ') compounds of the formula X' r GCH, CH3 ο

G ”N

V-_f gch2/ Oh3

N (X ')

AT 406 583 B in which n is the number 1 or 2 and in which G and G11 those under (a '), and G14 the under (b1) have given meaning, where for G14 the meanings -CONH-Z and -CH2-CH (OH) -CH2ODO are excluded.

Examples of such connections are:

100)

101)

102)

CH3 CH3

CH, CHS. o / - \

CHs-N NH

Η - NN — CHj fr

X_ / * ch3 ch3 ch3 ch3

CH3 CHg

CH3 CH3 o /3\ / CHg-NN ch3 _n n — ci4 fr — 7 ^

V__I ~

CH3XCH3

CH3 CH3 0

CH3 CH2ch3^xch3 (Amin M)

N - CH, 0 ch3 ch3

Compositions of interest are those in which component (c) (ii) or component (c) (iii) (y) is a compound of the formula IV in which n is an integer from the range from 1 to 4, G and GrAre hydrogen and

G11 Hydrogen or C.rCi8-Alkyl and

G12when n = 1, a radical of the formula - (CjH2j-Si (Z ')2Z, where j is an integer from the range from 2 to 5, and Z 'and Z are independently Ci-C4-Alkyl or Ci-C4-Alkoxy mean, represents and

G when n = 2. a residue of an aliphatic dicarboxylic acid with 2 to 12 carbon atoms, which is represented by -COOZ12 may be substituted, where Z '2 Is CrC ^ -alkyl,

G12if n = 3, a residue of an aromatic tricarboxylic acid with 9 to 15 carbon atoms,

G12when n = 4, represents a radical of an aliphatic tetracarboxylic acid having 8 to 12 carbon atoms; Amines of particular technical interest from this class are those of the formulas

CH, «

O-fCH ^ -Si— OCaHg oc ^ (amine B)

(Amine C)

AT 406 583 Β

(Amine D) (Amine E) and esters of butane-1,2,3,4-tetracarboxylic acid with 2 units each of 1,2,2,6,6-pentamethyl-4hydroxypiperidine and C.13H27-OH (amine F);

Also of interest are compositions in which component (c) (ii) or component (c) (iii) (y) is a compound of the formula V, in which n is 2, G and G1 Are hydrogen,

G1'Represents hydrogen or methyl,

G13 Hydrogen or C.rC.8-Alkyl mean, and

G14 C.2-C8-Alkylene or 1-oxo-C2-C8is -alkylene; an amine of particular technical interest from this class is the compound of the formula

Compounds of formula VIIC, wherein n is 1, G, G1 and G17 Are hydrogen,

G11 Means hydrogen or methyl, and

T4 and t2 together with the C atom that binds them, a C5-C14-Cycloalkane ring form; an amine of particular technical interest from this class is the compound of

AT 406 583 B

(Amine H)

CHS.

- G1 CHa G * 7 i3.CHq

Γ —E — CH V üxJ _ ^> ^ 3

N-G11 or —E- (A> —N NG11

CH, CH3

CH, CH3 mean

G11 Is hydrogen or methyl,

G1 and G2 Denote hydrogen or together a substituent = 0,

E -O- or -NG13- is, AC2-C6-Alkylene and x are one of the numbers 0 or 1,

G13 Represents hydrogen, C ^ C ^ -alkyl or cyclohexyl,

G20when n = 1, equals G18, and when n = 2, a group -EBE- is, in which B is Cr-Ce-alkylene or by 1 or 2 groups -N (G.21) - interrupted C2-C8-alkylene means G21 Ci-C12-alkyl, cyclohexyl, benzyl or Ci-C4-Hydroxyalkyl or a group of the formula

is, or G21 a group of the formula

means;

Sterically hindered amines from this class of particular technical interest are the above-described compound (76) [= amine J] and the compounds of the formulas

AT 406 583 B

(Amines K and L);

Compounds of the formula X 'wherein n is 2, G.11 Hydrogen or methyl and G.14 C.2-C12-Alkylene means;

an amine of particular technical interest from this class is the above-described compound (100) [= amine M]; as

Oligomeric compounds with 2 to 10 repeating units, as obtained by reaction (i ') of g21_n o — H where G24 C.2-C5-Hydroxyaikyl means with an aliphatic C2ch3 ch3

C.12Dicarboxylic acid or a suitable reactive derivative such as the diester, the dichloride or the anhydride;

(Γ) of a linear oligomeric polyester from a dialcohol and butane-1,2,3,4-tetracarboxylic acid with 2,2,6,6-tetramethyl-4-hydroxypiperidine;

C.2-C5-Alkylene, T3 C 1 -C 4 alkyl or cyclohexyl, T4 Hydrogen or CrC ^ -alkyl, or T3 and Τ 'together C4-C6-Alkylene or C3-C5-Oxaalkylene mean;

(1 ') by H2NA-NH-A-NH2 with and

Br-A-Br, where AC2-C5-Alkylene means;

(m ') of compounds of the formula

CH3 CH, C.VC.* ^ - C - CH, I.

NH with epichlorohydrin;

CH3 CHg

AT 406 583 B (n ') of

are available, as well as those of the formula (o ')

CH,

- -CHj- C -CH2- CHOCH,

O = C ι

OR wherein about one third of the radicals R is -C2H5 have and the other is;

H3C CHg

-xQ-h

Η-, σ ch3 and m is a number from the range from 2 to 10

Oligomeric amines of particular technical interest include those of the formulas (m again denotes a number from the range from 2 to 10)

CH,

-O / - ^CH3 θ θ - / N -CF ^ -CHg- O - C CH2-CH2 C.

I ^ CH,

-O-CHa (CAS No. 65447-77-0; amine

N);

CH,

(CAS No. 70624-18-9; amine P);

AT 406 583 B

(Amine Q)

CH3 I ^ Ha — C-CHa — CH—

I o = c

OCHg

O = C i

OR (amine R), in which about one third of the radicals R the

Meaning of -C2H5 have and the other H3C.v CH3

-O'-n mean; a linear h3c ch3

Polyester with 2 to 10 repeating units from butane-1,2,3,4-tetracarboxylic acid and a dialcohol of the formula

HO O-CH ^ CHa-O CH3 qh

CH - C - CH V CH - C - CHF

CHj O/ CHa, in which the end groups and side chains are formed by esterification of the free carboxyl groups with 2,2,6,6-tetramethyl-4-hydroxypiperidine (amine S); a copolymer,

is built up (amine T); the

Reaction product of H2N- (CH2)2-NH- (CH2)2-NH2 with

CH, ; qjj and 1 each

and Br- (CH2)2-Br (amine U); as

AT 406 583 Β

CH,

Reaction product of the compound of the formula

CHg ^ YH,

CH2 - (CH ^ g II .0 - C - CHg

C-ER with

II

Epichlorohydrin (amine W).

The oligomeric amines are often mixtures of compounds which differ from one another with regard to their chain length.

The use of the amines A, B, C, D, E, F, G, H, J, K, L, Μ, N, 0, P, Q, R, S, T, U, V and W.

For the compositions according to the invention, the addition of sterically hindered amines whose molecular weight or average molecular weight Mn in the range from 500 to 10,000, especially in the range from 1,000 to 10,000. Particularly noteworthy among these are again those sterically hindered amines whose molecular weight or average molecular weight Mn is in the range from 1500 to 10000, for example in the range from 2000 to 7500.

Particularly noteworthy are those compositions according to the invention which contain as component (c) (ii) or as component (c) (iii) (y) two or more compounds of the sterically hindered amine type.

Particularly preferred are compositions containing as component (c) (ii) or as component (c) (iii) (y) a compound from the group of sterically hindered amines, in which the molecular weight is greater than 1000 and the compound at least one radical of formula VI or VI '

contains where

R.13 Means hydrogen or methyl

Very particularly preferred are compositions containing as component (c) (ii) or as component (c) (iii) (y), a compound from the group of sterically hindered amines, in which the molecular weight is greater than 1000 and the compound is at least one Radical of the formula VI or VI 'and a radical of the formula VII

(VT) (VH)

AT 406 583 B contains, wherein

R.13 Means hydrogen or methyl.

Compositions containing, as component (c) (ii) or as component (c) (iii) (y), a linear or cyclic condensation product prepared from N, N'-bis (2,2,6,6 -tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro1,3,5-triazine [Chimassorb® 944LD (Ciba-Geigy), amine P in the description above]; or a condensation product prepared from 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropyl -amino) ethane [Chimassorb®119FL / 10 (Ciba-Geigy), compound no. 76].

The sterically hindered amines mentioned are known compounds; many of them are commercially available.

Compositions containing phenolic antioxidants of the formula ΙΓ as component (c) (iii) (x) are of interest

wherein

A hydrogen, CrC 1-4 alkyl, C5-C12-Cycloalkyl, Phenyl-C, -C4-alkyl, phenyl or a group -CH2-SR12 or means

DCrC.24-Alkyl, C5-C12-Cycloalkyl, phenyl-CrC4-alkyl, phenyl or a group -CH2-SR12 means,

X is hydrogen, C ^ -C ^ -alkyl or one of the groups -CaH2a-Sq-Ri3, -CbH2 B-CO-ORi4,

-CbH2 B-CO-N (R16) (R17), -CHaNiR ^ XR ^), -s

OH

G

-N

Oh is

R is hydrogen or a group of the formula -CO-CH = CH2 is,

G * for hydrogen or CrC12-Alkyl stands,

R12 C 1-6 alkyl, phenyl or a group - (CH2)c-CO-OR15 or -CH2CH2OR20 means,

Ri3 Hydrogen, C1 -C4 -alkyl, phenyl, benzyl or a group

OH

AT 406 583 B or - (CH2)c-CO-OR15 or -CH2-CH2-OR20 means,

R14 Cj-Cso-alkyl or one of the groups -CHR18-CH2-SR19,

OH or]3 means where QC2-C8-Alkylene,

C.4-C6-Thiaalkylen or a group -CH2CH2(OCH2CH2)d-is,

R.55 C.rC.24-Alkyl means

R.16 Hydrogen, Ci-C18-Alkyl or cyclohexyl,

R.17 Ci-Ci8-Alkyl, cyclohexyl, phenyl, phenyl substituted by C 1 -Cia -alkyl or

-CKCH ^ O-CO-CbHa, that

OH] 3, or R,6 and Ri7 together C4-C8-Alkylene, can be interrupted by -O- or -NH- mean, R18 Is hydrogen, C 1-4 alkyl or phenyl, R19 Ci-Cis-alkyl means R ^ hydrogen, CrC ^ -alkyl, phenyl, C2-C18-Alkanoyl or benzoyl is R21 CrC ^ alkyl, cyclohexyl, phenyl, through Ci-C18-Alkyl substituted phenyl or a group - (CH2) rNH-CH2-

OH means

R22 hydrogen, CrC.18-Alkyl, cyclohexyl, or a group -CH2

OH is, or

AT 406 583 B

R21 and R22 together C4-C8-Alkylene, which can be interrupted by -O- or -NH-, are Ra and R24 -S-CrCis-alkyl, a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, c is 1 or 2, d is 1 to 5, f is 2 to 8 and q is 1,2 , 3 or 4.

Component (c) (iii) (x) particularly preferably corresponds to compounds of the formula ΙΓ in which

A is hydrogen, CrCs-alkyl, cyclohexyl, phenyl or a group -CH2-R23 or

D CrCe-alkyl, cyclohexyl, phenyl or a group -CH2-R24 means,

X hydrogen, Ci-C8-Alkyl or one of the groups -CaH2a-Sq-R13, -CbH2 B-CO-OR14,

G * D or ^ 24

OH

R.13 CrC ^ -alkyl, phenyl or a group - (CH2)c-CO-OR15 means,

R.14 C.rC.18-Alkyl or a group -QO-CO-CbH2 B

OH means where QC2-Cs-Alkylene, -CH2-CH2-NS2CH2 or a group

-CH2CH2(OCH2CH2) d- is

R15 CrCie-alkyl means

R.2i and Ra independently of one another are hydrogen or CrCi2-Alkyl or R2i and Ra together C4-C8-Alkylene, which can be interrupted by -O- or -NH-, mean, a is 1 or 2, b is 1 or 2, c is 1 or 2 and d is 1, 2 or 3 and

R.23 and R24 -S-CrC ^ -alkyl.

Compounds of the formula IF, in which v

A hydrogen, C ^ Ce alkyl, -CH2-R23 or a group means

D for hydrogen or CrC.18-Alkyl stands,

X for hydrogen, CrC ^ alkyl, -CH2-Ra or a group of the formula

AT 406 583 B

R.23 and R24 -S-Ci-C18-Alkyl.

Component (c) (iii) (x) can also be a tocopherol or vitamin E derivative, such as, for example, α-tocopherol, ß-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof. Of these, vitamin E itself (α-tocopherol) is preferred.

The component (c) (iii) (x) can also be an oligomeric phenolic antioxidant of the following type

represent wherein the average molecular weight is 600 to 700.

Compositions according to the invention containing a compound of the formula VIII as component (c) (iii) (x) are particularly preferred

represents where

R, CvCre-alkyl, C5-C12-Cycloalkyl, phenyl or Cy-Cg-phenylalkyl,

R.2 Hydrogen, CrC.18-Alkyl, Cs-C12-Cycloalkyl, phenyl or Cy-Cg-phenylalkyl,

R.3 Represents hydrogen or methyl, 45 ,,. - CH, —CH—utt

QCmH2m or z 1 means

R.14 Represents Ci-Cg-alkyl,

X is oxygen or -NH-, m is the number 0, 1, 2 or 3, p is the number 1, 2 or 4, and when p is 1,

Ri5 Cs-C ^ alkyl or C5-C12-Cycloalkyl, and when p is 2 and X is oxygen,

R15 C2-C8Alkylene or C interrupted by oxygen or sulfur4-C8-Alkylene means;

and when p is 2 and X is -NH-,

AT 406 583 B

R.15 a direct bond, C2-C8Alkylene or C interrupted by oxygen or sulfur4C.8Is -alkylene, and when p is 4, R15 C.4-C10-Alkante tetrayl.

The preferred compounds of the formula I or II as component (c) (iii) (x) in the compositions according to the invention are the same as for component (c) (i).

Particularly preferred are compositions containing, as component (c) (iii) (x), compounds of the formula I, II or VIII, in which Rt and R2 is tert-butyl, and m is 2

Compositions containing as component (c) (iii) (x) Irganox®1010 (Ciba-Geigy), Irganox®MD 1024 (Ciba-Geigy) and Irganox®1076 (CibaGeigy) are of very special interest.

Irganox®1010 (CibaGeigy) lrganox®MD 1024 (Ciba-

ch2-ch2- c -

O nC ·,

Irganox®1076 (CibaBpreferred are also compositions containing as component (c), component (i) or component (iii).

Of very special interest are compositions in which component (b) tris- (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butyl-6-methyl) ethyl phosphite or a compound of the formula Ph- 3 or Ph-11

AT 406 583 B

(Ph-11) means;

component (c) (i) is a compound of the formula I in which n is 3,

Ri and R2 mean tert-butyl,

R.3 Hydrogen is and

represents;

components (c) (ii) and (c) (iii) (y) linear or cyclic condensation products prepared from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4- tert-octylamino-2,6-dichloro1,3,5-triazine; or a condensation product made from 2-chloro-4,6-di- (4-n-butylamino1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino ) mean ethane; and component (c) (iii) (x)

AT 406 583 B (CH3)3C.

(CH3)3C represents or;

Components (b) and (c) are suitable for stabilizing polyolefins that are in constant contact with extracting media.

Examples of polyolefins are:

1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins such as, for example, cyclopentene or norbomene; also polyethylene (which can optionally be crosslinked), for example High density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene ( LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie polymers of monoolefins, as mentioned by way of example in the preceding paragraph, in particular polyethylene and polypropylene, can be produced by various processes, in particular by the following methods:

a) radical (usually at high pressure and high temperature).

b) by means of a catalyst, the catalyst usually containing one or more metals from group IVb, Vb, VIb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either π- or σ-coordinated. These metal complexes can be free or fixed on a carrier, for example on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization, or other activators can be used, such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups la, lla and / or purple. The activators can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), eg mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

3rd Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as Ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and blends thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers. Ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their

AT 406 583 B

Salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethyl denorbomene; also mixtures of such copolymers with one another and with the polymers mentioned under 1), for example Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers and alternating or random polyalkylene / carbon monoxide copolymers and their mixtures with other polymers such as polyamides.

4th Hydrocarbon resins (e.g. C5-C9) including hydrogenated modifications thereof (e.g. tackifier resins) and mixtures of polyalkylenes and starch.

Preferred polyolefins are polyethylene or polypropylene and their copolymers with monolefins and diolefins.

Particularly noteworthy is the effect of the stabilizer mixture comprising a component (b) and a component (c) against oxidative and thermal degradation of polyolefins as occurs during the processing of thermoplastics. The polyolefins stabilized in this way are also characterized by excellent chemical resistance to extracting media that are in constant contact.

Component (b) is preferably added to the polyolefin to be stabilized in an amount of 0.02 to 0.6%, in particular 0.05 to 0.2%, and component (c) in an amount of 0.02 to 1, 0%, in particular 0.05 to 0.3%, is added, based on the weight of the polyolefin to be stabilized.

If component mixture (c) (iii) is used as component (c), component (c) (iii) (x) is preferably added to the polyolefin to be stabilized in an amount of 0.02 to 0.5%, in particular 0.05 to 0.2%, and component (c) (iii) (y) in an amount of 0.02 to 1.0%, in particular 0.05 to 0.3%, based on the weight of the material to be stabilized Polyolefins.

In addition to components (b) and (c), the compositions according to the invention can contain further costabilizers (additives), such as, for example, the following:

1. Antioxidants

1.1. Alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol,

2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di- cyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dictadecyM-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, linear or branched in the side chain nonylphenols such as 2,6-Di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec- 1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio -methyl-4onylphenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4- octadecyl-oxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl 4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, ß-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thio-bis (6-tert-butyl-3 -methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec.-amylphenol), 4,4 ' -Bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkvlidene bisphenols, e.g. 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylene bis [4-methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol ), 2,2'-methylene-bis (4,6-di-teA.t-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene -bis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methyl-bis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis (2, 6-di-tert-butylphenol), 4,4'-methylene-bis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl ) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1, 3-tris (5-tert-butyl-4hydroxy-2-methylphenyl) butane , 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyW-hydroxyphenyl) butyrate], Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene, bis [2- (3 '-tert-butyl-2' -hydroxy-5'-methylbenzyl) -6-tert42

AT 406 583 B

Ethylene glycol, triethylene glycol,

Ethylene glycol, triethylene glycol, butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) -butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-ndodecylmercapto-butane, 1,1,5-tetra- (5-tert-butyl-4-hydroxy -2-methylphenyl) pentane.

1.7. Ο-, N- and S-benzyl compounds, e.g. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4-tert-butyl-3-hydroxy2,6-dimethyl-benzyl ) dithioterephthalate, bis (3,5Hji-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxy-benzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) ) malonate, di-dodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethylbutyl) phenyl] -2 , 2bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate

1.9. Hydroxybenzyl aromatics, e.g. 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6trimethylbenzo !, 1,4-bis (3,5-di-tert- butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -phenol.

1.10. Triazinverbindunqen, e.g. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxy-anilino) 1,3.5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert -butyl-4-hydroxyanilino) -1,3,5-triazine, octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4 , 6-Tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) - isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -iso-cyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl-ethyl ) -1,3,5-triazine, 1,3,5-Tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-Tris (3,5-dicyclo-hexyl- 4-hydroxybenzyl) isocyanurate

1.11. Benzyl phosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl -5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.

1.12. Acylaminophenols, for example 4-hydroxylauric anilide, 4-hydroxystearic anilide, N- (3,5 di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester.

1.13. Esters of ß- (3,5-di-tert-butyl-4-hvdroxvphenvO-propionic acid with mono- or polyhydric alcohols, such as with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9 nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodi-ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) - isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadeca-noi, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabi-cyclo- [2.2. 2] octane.

1.14. Esters of ß- (5-tert-Butvl-4-hvdroxv-3-methvlphenyl) propionic acid with monohydric or polyhydric alcohols, such as with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'Bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15. Esters of ß- (3.5-dicyclohexyl-4-hydroxylphenyl) propionic acid with monohydric or polyhydric alcohols, such as with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,

Neopentyl glycol, thiodiethylene glycol, diethylene glycol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxymethyl-1-phospha-2,6,7- - [2.2.2] octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenvlessic acid with monohydric or polyhydric alcohols, such as, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,

Neopentyl glycol, thiodiethylene glycol, diethylene glycol, tris (hydroxyethyl) isocyanurate, N.N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6, 7-trioxabicyclo [2.2.2] octane.

1.17. Amides of ß- (3.5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylene diamine, N, N'- Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, N, N'-bis [2- ( 3- [3,5-di-tert-butyl-4-hydroxyphenyl ] propionyloxy) ethyl] oxamide.

1.18. Ascorbic acid (vitamin C).

1,2-propanediol, pentaerythritol,

AT 406 583 B

1.19. Aminic antioxidants such as N.N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butylp-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, N, N ' -Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyI) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyi- p-phenylenediamine, N, N'-di- (naphthyl-2) -p-phenylenediamine, Nisopropyl-N '-phenyl-p-phenylenediamine, N- (1,3-di-methyl-butyl) -N' -phenyl -p-phenylenediamine, N- (1Methyl-heptyl) -N '-phenyl-p-phenylenediamine, N-Cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluene-sulfonamido) -diphenyl-amine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine,

Diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p, p'-Ditert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di- (4-methoxyphenyl) amine, 2 , 6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4'-diamino-diphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diamino- diphenyl-methane, 1,2-di - [(2-methyl-phenyl) amino] -ethane, 1,2-di- (phenylamino) -propane, (o-tolyl) -biguanide, di- [4- (1 ', 3'-dimethylbutyl) phenylamine, tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isopropyl / isopropyl diphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butyl / tert-octylphenothiazines , Mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6, 6-tetramethyl-piperidin-4-yl-hexamethylene-diamine, bis- (2,2,6,6-tetra-methylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2 , 2,6,6-tetramethylpi-peridin-4-ol.

2. UV absorbers and light stabilizers

2. 1. 2- (2 '-HvdroxyphenvD-benzotriazoles. Such as 2- (2'-Hydroxy-5'-methyiphenyl) -benzotriazoI, 2- (3', 5'-di-tert-butyl-2 '-hydroxyphenyl) -benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' - (1,1,3,3-tetramethylbutyl) phenyl) -benzotriazole, 2 - (3 ', 5'-Di-tert-butyl2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' -methylphenyl) -5-chlorobenzotriazole , 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4Toctoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2' -hydroxyphenyl) -benzotriazole, 2- (3 ', 5' -Bis (a, adimethylbenzyl) -2 '-hydroxyphenyl) - benzotriazole, mixture of 2- (3'-tert-butyl-2'-hydroxy-5 '- (2octyloxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5' - [2 - (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5- chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonyiethyl ) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3,-Dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2isooctyloxycarbonylethyl) phenyi-benzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6benzotriazol-2-yl-phenol]; transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'hydroxy-phenylj -benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2- with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzo-triazol-2-yl-phenyl.

2.2. 2-Hydroxvbenzophenone, such as 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyl-oxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy derivative.

2.3. Esters of optionally substituted benzoic acids, such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4- 2,4-di-tert-butylphenyl hydroxybenzoate, 3,5-di-tert-butyl-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid re-2-methyl-4,6-di-tert-butylphenyl ester.

2.4. Acrylates, such as α-cyano-ß, ß-diphenylacrylate ethyl ester or isooctyl ester, a-carbomethoxycinnamate, alpha-cyano-beta-methyl-p-methoxycinnamate or butyl ester, alpha-carbomethoxy-p-methoxycinnamate, N- ( ß-Carbo-methoxy-ß-cyanovinyl) 2-methylindoline.

2.5. Nickel compounds, such as, for example, nickel complexes of 2,2'-thio-bis [4- (1,1,3,3-tetramethylbutyß-phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of 244

AT 406 583 B

Hydroxy-4-methyl-phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, such as bis (2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, bis (2,2,6,6-tetramethyl-piperidin-4-yl) succinate, bis ( 1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, n-butyl-3,5- di-tert-butyl-4-hydroxybenzylmalonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl2.2.6.6-tetramethyl-4-hydroxypiperidine and succinic acid. Condensation product of N, N'Bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-striazine, tris (2.2 , 6,6-tetra-methyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetraoate, 1,1- (1,2 -Ethandiyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6tetramethylpipendin, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, Bis (1,2,2,6,6-pentamethylpiperidyl) 2- n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7, 9,9-tetramethyl-1,3,8triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy2.2.6.6 - tetramemylpiperidyl) succinate, condensation product of N, N'-bis (2,2,6,6-tetramethyl-4piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, Condensation product of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3aminopropylamino) ethane. Condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethyl-piperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) -ethane, 8-acetyl-3-dodecyl7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6, 6-tetra-methyl-4piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) -pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy and 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, Condensation product from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product from 1,2-bis ( 3aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-pi-peridyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-Undecyl-7,7,9,9-tetramethyl-1-oxa3,8-diaza-4-oxo-spiro [4.5] decane, reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl- 1oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin.

2.7. Oxalic acid diamides, such as 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-O.S'-di-tert-butyl-oxanilide ^^ '- di-dodecyloxy -S.S'-di-tert-butyl-oxanilide ^ -ethoxy ^ '- ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.

2.8. 2- (2-Hydroxvphenvl) -1.3,5-triazines, such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl 6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyl-oxyphenyl) -4,6-bis (4-methylphenyl) 1,3,5-triazine , 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy3-butyloxy-propyloxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-hydroxy-3-octyl-oxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy ) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3,5-triazine, 2 (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

3rd Metal deactivators, such as, for example, N.N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyihydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4 -hydroxyphenyl-propionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, N, N'-di-acetyl-adipic acid dihydrazide , N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihydrazide.

4th Phosphites and phosphonites, such as Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) -phosphite, di-tert-butylphenyl-penthrosphite, di-tert-butylphenyl-but-2,4-phosphite-di-tert-butylphenyldiphosphite, di-tert-isodecyl pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4methylphenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl6-methylphenyl) pentaerythritol diphosphite, bis- (2,4 , 6-tri-tert-butylphenyl) 45

AT 406 583 Β pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl -12H-di-benz [d, g] -1,3,2dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz- [d, g] -1, 3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) -methyl phosphite, bis- (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

5. Hydroxylamines such as N, N-dibenzylhydroxylamine, Ν, Ν-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, Ν, Ν-ditetradecylhydroxylamine, N, NDihexadecylhydroxylamine, N, N-hexadecylhydroxyl-hydroxadecyl-N-hexadecyl-N-hexadecyl-hydroxadecyl-hydroxy , N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.

6th Nitrones such as N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-Oc-tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl -nitrone, N-hexadecyl-alphapentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, NOcatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitron , N-octadecyl-alphahexadecyi-nitrone, nitrones derived from Ν, Ν-dialkylhydroxylamines produced from hydrogenated tallow fatty amines.

7th Thiosynergists such as di-lauryl thiodipropionate or distearyl thiodipropionate.

8th. Peroxide-destroying compounds, such as, for example, esters of β-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl-pentecyldisulfide (mercapto) mercapto-mercapto-mercapto (pentecyl-disulfide) (.

9. Polyamide stabilizers, such as copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na - Ricinoleate, K palmitate, antimony catecholate or tin catecholate.

11. Nucleating agents, such as, for example, inorganic substances such as, for example, talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably of alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts such as, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).

12th Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers from other natural products, synthetic fibers.

13. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, leveling aids, optical brighteners, flame retardants, antistatic agents, blowing agents.

14th Benzofuranones or indolinones, such as in US-A-4,325,863, US-A-4,338,244. US-A-5,175

312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A0 589 839 or EP- A-0 591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [ 4- (2-steamer 1-oxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7 di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran -2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzof uran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl -4-piva-loyloxyphenyl) -5,7- di-tert-butyl-benzofuran-2-one.

With the exception of the fillers and reinforcing agents (item 12 of the list), the costabilizers are added to the polyolefin, for example in concentrations of 0.01 to 10%, based on the total weight of the polyolefin to be stabilized.

The fillers and reinforcing agents (item 12 of the list) such as talc, calcium carbonate, mica or kaolin are added to the polyolefin, for example in concentrations of 0.01 to 40%, based on the total weight of the polyolefin to be stabilized.

The fillers and reinforcing agents (item 12 of the list) such as metal hydroxides, in particular aluminum hydroxide or magnesium hydroxide, are added to the polyolefin, for example in concentrations of 0.01 to 60%, based on the total weight of the polyolefin to be stabilized.

Carbon black as a filler is expediently added to the polyolefin in concentrations of 0.01 to 5%, based on the total weight of the polyolefin to be stabilized.

AT 406 583 B

Glass fibers as a reinforcing agent are expediently added to the polyolefin in concentrations of 0.01 to 20%, based on the total weight of the polyolefin to be stabilized.

In addition to components (a), (b) and (c), further preferred compositions contain further additives, in particular UV absorbers and light stabilizers (item 2 of the list); Amides of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (metal deactivators, item 1.17 of the list); Nucleating agents (item 11 of the list) and / or fillers and reinforcing agents (item 12 of the list).

Of particular interest as additional additives are metal deactivators such as, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine [Irganox® MD1024 (Ciba-Geigy)] or N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyl-oxy) ethyl] oxamide [Naugard® XL-1 (Uniroyal)].

Components (b) and (c), and any other additives, are incorporated into the polyolefin by known methods, for example before or during molding or by applying the dissolved or dispersed stabilizer mixture to the polyolefin, optionally with subsequent evaporation of the solvent . The stabilizer mixture of components (b) and (c) can also be added to the polyolefins to be stabilized in the form of a masterbatch which contains them, for example, in a concentration of 2.5 to 25% by weight.

The stabilizer mixtures of components (b) and (c) can also be added before or during the polymerization or before the crosslinking.

The stabilizer mixtures of components (b) and (c) can be incorporated into the polyolefin to be stabilized in pure form or encapsulated in waxes, oils or polymers.

Components (b) or (c) or their mixtures can also be sprayed onto the polyolefin to be stabilized. They are able to dilute other additives (for example the conventional additives specified above) or their melts, so that they can also be sprayed onto the polyolefin to be stabilized together with these additives. The addition by spraying on during the deactivation of the polymerization catalysts is particularly advantageous, with, for example the steam used for deactivation can be used for spraying.

In the case of spherically polymerized polyolefins, for example, it can be advantageous to apply components (b) or (c), optionally together with other additives, by spraying.

The polyolefins stabilized in this way can be used in a wide variety of forms, in particular as thick-layer polyolefin moldings that are in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkaline solutions or C ^ C ^ alcohols, such as pipes, films, geomembrane, tapes, profiles or tanks.

The present invention also relates to a method for stabilizing thick-layered polyolefin moldings which are in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkalis or CrC4-Alcohols, which is characterized in that at least one mixture containing a component (b) and a component (c) is incorporated into or applied to them.

A method is preferred for stabilizing thick-layer polyolefin moldings which are in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkalis or CiC ^ alcohols, in which the thick-layer polyolefin moldings have a layer thickness of 1 to 50 mm, in particular 1 to 30 mm , for example 2 to 10 mm.

Also of particular interest is a process for stabilizing thick-layer polyolefin moldings which are in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkalis or CrC ^ alcohols, in which the thick-layer polyolefin moldings are pipes or geomembrane.

Geomembranes are films that are used, for example, in landfills and have a lifespan of up to 300 years.

Aqueous salt solutions are, for example, common salt solution (brine) or sodium sulfate solution.

Dilute aqueous alkalis are, for example, aqueous sodium hydroxide solution (NaOH), aqueous potassium hydroxide solution (KOH), aqueous ammonia solution, aqueous sodium bicarbonate solution or aqueous soda solution.

CrC ^ alcohols are, for example, methanol, ethanol, isopropanol or butanol.

AT 406 583 B

A preferred embodiment of the present invention is therefore the use of a mixture containing a component (b) and a component (c) for stabilizing thick-layered polyolefin moldings that are in permanent contact with water, chlorinated drinking water, aqueous salt solution, dilute aqueous alkalis or Ci-C4-Alcohols are available.

The following examples further illustrate the invention. Parts or percentages relate to weight.

Example 1: Stability of polyethylene stabilized with a component (b) and a component (c) (i) which is in permanent contact with water.

The unstabilized medium density polyethylene (PE-MD) used has the material properties summarized in Table 1 10.

<td colspan="2">Table 1: Material properties of the</td><td colspan="2">Polyethylene at 23 ° C</td>

<td>characteristic</td><td>value</td><td>unit</td><td>Test method</td>

<td>density</td><td> 0,934</td><td>g / cmJ</td><td>ISO 1872</td>

<td>Yield stress cs</td><td> 18</td><td>N / mm2</td><td>ISO 6259</td>

<td>Elongation €s</td><td> 9</td><td> %</td><td>ISO 6259</td>

<td>Elongation at break Gr</td><td> >600</td><td> %</td><td>ISO 6259</td>

<td>Tangents mod ul</td><td> 550</td><td>N / mm2</td><td>ISO 6259</td>

<td>hardness</td><td> 58</td><td>Shore D</td><td>ISO 868</td>

<td>Vicat temperature</td><td> 118</td><td>° C</td><td>ISO 306 A-50</td>

<td>Crystallite melting temperature</td><td> 123-127</td><td>° C</td><td>DSC</td>

0.1% by weight calcium stearate and the stabilizers listed in Table 2 are added dry to the polyethylene polymer removed directly from the reactor and incorporated in a cardboard painters' mixer (type 20) for two minutes (Examples 1a, 1b and 1c).

Table 2: _

<td>example</td><td>stabilizer</td><td>Amount (wt.%)</td><td>molar mass (g / mol)</td><td>M.p. (° C)</td>

<td>Example 1a</td><td>Igrafos 168aj Irganos 1010b)</td><td> 0,1 0,1</td><td> 647 1178</td><td> 180-185 110-125</td>

<td>Example 1b</td><td>Igrafos 168a) Irganos 1330c)</td><td> 0,1 0,1</td><td> 647 775</td><td> 180-185 241-245</td>

<td>Example 1c</td><td>Igrafos 168a)Irganos 3114φ</td><td> 0,1 0,1</td><td> 647 784</td><td> 180-185 218-223</td>

a) Irgafos® 168 (Ciba-Geigy) means tris (2,4-di-tert-butylphenyl) phosphite (formula Ph-2, page 7).

b) Irganox® 1010 (Ciba-Geigy) means the pentaerythritol ester of 3- (3,5-di-tert-butyl-420 hydroxyphenylpropionic acid (formula see page 49).

c) Irganox® 1330 (Ciba-Geigy) means 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6trimethylbenzene (formula see page 12).

d) Irganox®3114 (Ciba-Geigy) means 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (formula see page 13).

The stabilized polyolefin is homogenized in an extruder from Dolci, Milan (screw geometry: L / d = 35, screw speed: 55 revolutions / minute, maximum nozzle temperature: 190 ° C., cooling of the feed zone) and processed into approx. 60 kg of granules per formulation . For the extraction tests in water, the granules of the individual formulations (Examples 1a, 1b and 1c) are made using the methods specified in Table 3

Machine parameters

Table 3: Machine parameters for test panels

<td>Melting time (min.)</td><td> 4</td>

<td>Pressing temperature (° C)</td><td> 180</td>

<td>Pressing force (kN)</td><td> 100</td>

<td>Pressing time (min)</td><td> 4</td>

<td>Cooling time (min)</td><td> 5</td>

<td>Cooling medium</td><td>water</td>

AT 406 583 B pressed with a bench press 200 mm by 150 mm by 2 mm large test plates. In order to facilitate the demolding of the test plates, the pressing process takes place between two aluminum foils.

The stabilizer extraction tests are carried out with deionized water. The temperature of the extraction vessels is controlled in a convection oven from Heraeus (Hanau, Germany) with a maximum temperature deviation of 1.5 ° C. Glass vessels are used for the extraction attempts below the boiling point of the water. At a water temperature of 105 ° C, pressure vessels made of stainless steel are used. Because of the danger of a

With stabilizer oversaturation of the water, the amount of liquid for the experiments is set at approx. 400 ml with approx. 70 g of polymer and the water is replaced by fresh water at regular intervals, namely after each sample is taken.

The test plates are exposed to the test conditions described above for up to 16032 hours (668 days). After completion of the extraction attempts, the

Test plates the oxidation temperature (Tox) certainly. The oxidation temperature is determined using a DuPont instrument 910 Differential Scanning Calorimeter from TA Instruments (Alzenau, Germany) and with a sample amount of 5 to 10 mg and describes the beginning of the thermal decomposition of the polyolefin sample in the dynamic test. These dynamic tests are carried out in open aluminum crucibles with a heating rate of

10 ° C / minute and a starting temperature of 30 ° C carried out in a normal atmosphere. For the temperature range up to 260 ° C, indium (melting temperature Ts = 156.8 ° C; Enthalpy of fusion? HS. = 26.8 J / g) was used. The higher the oxidation temperature (T.ox), the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water, which is in constant contact with the polyolefins. The results are summarized in Tables 4 and 5

Table 4: Extraction tests with water at 95 ° C

<td rowspan="2">Extraction time (Hours)</td><td colspan="3">Oxidation temperature (T.ox) in ° C</td>

<td>Example 1a</td><td>Example 1b</td><td>Example 1c</td>

Table 5: Extraction tests with water at 105 ° C

<td rowspan="2">Extraction time (Hours)</td><td colspan="3">Oxidation temperature (T.ox) in ° C</td>

<td>Example 1a</td><td>Example 1b</td><td>Example 1c</td>

Example 2: Stability of polyethylene stabilized with a component (b) and a component (c) (iii) which is in permanent contact with water.

In analogy to Example 1, the stabilizers shown in Table 6 are incorporated into the medium density polyethylene (PE-MD) (Examples 2a, 2b and 2c). Table 6:

<td>example</td><td>stabilizer</td><td>Amount (wt.%)</td><td>molar mass (g / mol)</td><td>M.p. (° C)</td>

<td>Example 2a</td><td>Irgafos 168aJ</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td></td><td>Irganox 1010b)</td><td> 0,10</td><td> 1178</td><td> 110-125</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 2b</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Chimassorb 944LDC)</td><td> 0,20</td><td> >2500</td><td> 120-150</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 2c</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Chimassorb 119FL / 10d)</td><td> 0,20</td><td> 2286</td><td> 115-150</td>

AT 406 583 B

a) Irgafos® 168 (Ciba-Geigy) means tris (2,4-di-tert-butylphenyl) phosphite (formula Ph-2, page 7).

b) Irganox® 1010 (Ciba-Geigy) means the pentaerythritol ester of 3- (3,5-di-tert-butyl-4-hydroxyphenyl propionic acid (formula see page 49).

c) Chimassorb®944LD (Ciba-Geigy) means linear or cyclic condensation products made from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino2,6-dichloro -1,3,5-triazine (formula amine P, page 40).

d) Chimassorb® 119FL710 (Ciba-Geigy) means a condensation product prepared from 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3aminopropylamino) ethane (Formula 76, Amine J, pages 28/29).

In analogy to Example 1, the stabilized polyethylene test plates are exposed to the water extraction conditions described in Example 1 at 95 ° C. for up to 16030 hours (668 days). After completion of the extraction tests, the tensile strength of the test plates is determined in mega-Pascal (MPa). The tear strength is measured using the standard S2 according to DIN 53504. The tensile tests are carried out at room temperature at the earliest 24 hours after the respective samples have been removed from the water bath. The take-off speed is 200 mm / minutes. The greater the tensile strength values, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water, which is in constant contact with the polyolefins. The results are summarized in Table 7.

Table 7: Extraction tests with water at 95 ° C

<td rowspan="2">Extraction time (Hours)</td><td colspan="3">Tear strength in Mpa</td>

<td>Example 2a</td><td>Example 2b</td><td>Example 2c</td>

Example 3: Stability of polyethylene stabilized with a component (b) and a component (c) (iii) which is in permanent contact with water.

In analogy to Example 1, the stabilizers shown in Table 8 are incorporated into the medium-density polyethylene.

AT 406 583 B

Table 8:

<td>example</td><td>stabilizer</td><td>lot (Wt%)</td><td>molar mass (g / raol)</td><td>M.p. (° C)</td>

<td>Example 3a</td><td>Irgafos 168a)Irganox 1010b)</td><td> 0,10 0,10</td><td> 647 1178</td><td> 180-185 110-125</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3b</td><td>Irganox 1010 ^</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Tinuvin 622c)</td><td> 0,20</td><td> >2500</td><td> 55-70</td>

<td></td><td>Irgafos 168 * '</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3c</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Cyasorb 3346d></td><td> 0,20</td><td> 1500-1800</td><td> 110-130</td>

<td></td><td>Irgafos 168 ^</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3d</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Hostavin NSO *5</td><td> 0,20</td><td> >1500</td><td> 100-130</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3e</td><td>Irganox 10I0b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Uvasorb HA 88 ^</td><td> 0,20</td><td> 3300</td><td> 120-150</td>

<td></td><td>Irgafos 168 * '</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3f</td><td>Irganox 1010 ^</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Dastib 1082 * 1</td><td> 0,20</td><td> 2970</td><td> 162-181</td>

<td></td><td>Irgafos 168 * 1</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3g</td><td>Irganox 1010b)</td><td> 0.05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Uvinul 5050 * Ί</td><td> 0,20</td><td> 3500</td><td> 95-125</td>

AT 406 583 B

Table 8; (Continuation)

<td>example</td><td>stabilizer</td><td>lot (Wt%)</td><td>molar mass (g / raol)</td><td>M.p. (° C)</td>

<td></td><td>Irgafos 168 »</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3h</td><td>Irganox 1010a) b) c)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Irgafos 168 »</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3i</td><td>Irganox 1010 »</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Irgafos 168 »</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3j</td><td>Irganox 1010 * ° Uvasil 299 »</td><td> 0,05 0,20.</td><td> 1178 1100-2500</td><td> 110-125</td>

<td></td><td>Irgafos 168 »</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3k</td><td>Irganox 1010 »</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Light protection fabric UV-31 »</td><td> 0,20</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 31</td><td>Irganox 101Öb></td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Chimassorb 944 ° »</td><td> 0,20</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos 168 »</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 3m</td><td>Irganox 1010 »</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Chimassorb 119 FL / 10 »</td><td> 0,20</td><td> 2580</td><td> 100-125</td>

a) Irgafos® 168 (Ciba-Geigy) means tris (2,4-di-tert-butylphenyl) phosphite (formula Ph-2, page 7) b) Irgafos®1010 (Ciba-Geigy) means the pentaerythritol ester of 3- ( 3,5-di-tert-buryl-4-hydroxyphenylpropionic acid.

c) Tinuvin®622 (Ciba-Geigy) means poly (N-ß-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidyl succinate).

AT 406 583 B

d) Cyasorb® UV 3346 (Cytec) means a compound of the formula 92.

e) Hostavin®N30 (Hoechst) means a reaction product of the compound of the formula

with epichlorohydrin (amine W).

f) Uvasorb®HA 88 (Sigma) means a compound of the formula 95.

g) Dastib® 1082 (Slovakia) means a compound of the formula 92 '.

AT 406 583 B

h) Uvinul®5050 (BASF) means a compound of the formula A '.

i) MARK®LA 63 (Asahi Denka) means a compound of the formula B '.

j) MARK®LA 68 (Asahi Denka) means a compound of the formula C '.

CHjj —— »O

-C-CHj-CH- co oo

A CHjHaC A jj * ^ * 3 O — r—

- CW — CWj "- C -1 O - '- CHj' ·· C »'/ \ /

Γ 0

-CH3 '«« 3

CH — CCH3 chj — o (C)

k) Uvasil®299 (Great Lakes Chemicals) means a compound of the formula D '.

AT 406 583 B

I) light protection substance UV-31 (Leuna) means a compound of the formula E '

wherein R is octadecyl or 2)2,6>6-tetramethyl-4-piperidyl represented.

m) Chimassorb®944LD (Ciba-Geigy) means linear or cyclic condensation products prepared from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino2,6-dichloro - 1,3,5-triazine.

n) Chimassorb® 119FL / 10 (Ciba-Geigy) means a condensation product prepared from 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamemylpiperidyl) -1,3,5 -triazine and 1,2-bis (3aminopropylamino) ethane.

In analogy to Example 1, the stabilized polyethylene test plates are exposed to the water extraction conditions described in Example 1 at 95 ° C. for up to 16030 hours (668 days). After completion of the extraction tests, the elongation at break of the test plates is determined in percent. The elongation at break is measured using the standard S2 according to DIN 53504. The tensile tests are carried out at room temperature no earlier than 24 hours after the respective samples have been removed from the water bath. The take-off speed is 200 mm / minute. The greater the elongation at break values, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water, which is in constant contact with the polyolefins. The results are summarized in Table 9.

Table 9: Extraction tests with water at 95 ° C

<td rowspan="2">Examples</td><td colspan="5">Elongation at break in percent after x hours of extraction time</td>

<td>Example 3a</td><td> 840</td><td> 651</td><td> 592</td><td> 598</td><td> 581</td>

<td>Example 3b</td><td> 845</td><td> 675</td><td> 642</td><td> 601</td><td> 601</td>

<td>Example 3c</td><td> 841</td><td> 762</td><td> 678</td><td> 685</td><td> 620</td>

<td>Example 3d</td><td> 835</td><td> 775</td><td> 766</td><td> 671</td><td> 615</td>

<td>Example 3e</td><td> 836</td><td> 681</td><td> 634</td><td> 645</td><td> 617</td>

<td>Example 3f</td><td> 840</td><td> 721</td><td> 635</td><td> 631</td><td> 618</td>

<td>Example 3g</td><td> 842</td><td> 702</td><td> 688</td><td> 679</td><td> 619</td>

<td>Example 3h</td><td> 839</td><td> 684</td><td> 627</td><td> 623</td><td> 621</td>

<td>Example 3i</td><td> 838</td><td> 681</td><td> 679</td><td> 595</td><td> 619</td>

<td>Example 3j</td><td> 846</td><td> 709</td><td> 635</td><td> 625</td><td> 624</td>

<td>Example 3k</td><td> 850</td><td> 711</td><td> 630</td><td> 576</td><td> 622</td>

<td>Example 3I</td><td> 851</td><td> 842</td><td> 805</td><td> 801</td><td> 723</td>

<td>Example 3m</td><td> 849</td><td> 815</td><td> 733</td><td> 702</td><td> 675</td>

Example 4: Stability of polyethylene stabilized with a component (b) and a component (c) (iii) which is in permanent contact with water.

In analogy to Example 1, the stabilizers shown in Table 10 are incorporated into the medium-density polyethylene.

AT 406 583 B

Table 10: (continued)

<td>example</td><td>stabilizer</td><td>lot (Wt%)</td><td>molar mass (g / mol)</td><td>M.p. (° C></td>

<td>Example 4a</td><td>Irgafos 168a)Irganox ΙΟΙΟ15/</td><td> 0,10 0,10</td><td> 647 1178</td><td> 180-185 110-125</td>

<td></td><td>Irgafos 168a></td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 4b</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Chimassorb 944c)</td><td> 0,20</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos 168a></td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 4c</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Cyasorb 3346d></td><td> 0,20</td><td> 1500-1800</td><td> 110-130</td>

<td></td><td>Irgafos 168 *J</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 4d</td><td>Irganox ΙΟΙΟ * ^</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Uvasorb HA 88e)</td><td> 0,20</td><td> 3300</td><td> 120-150</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 4e</td><td>Irganox ΙΟΙΟ®</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Hostavin N30 °</td><td> 0,20</td><td> >1500</td><td> 100-130</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 4f</td><td>Irganox 1010b)</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Uvinul 5050 *></td><td> 0,20</td><td> 3500</td><td> 95-125</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 4g</td><td>Irganox 1010 ^</td><td> 0,05</td><td> 1178</td><td> 110-125</td>

<td></td><td>Chimassorb 119 FL / 10 «</td><td> 0,20</td><td> 2580</td><td> 100-125</td>

a) Irgafos® 168 (Ciba-Geigy) means tris (2,4-di-tert-butylphenyl) phosphite (formula Ph-2, page 7).

b) Irganox®1010 (Ciba-Geigy) means the pentaerythritol ester of 3- (3,5-di-tert-butyl-4-hydroxyphenylpropionic acid.

AT 406 583 B

c) Chimassorb®944 (Ciba-Geigy) means linear or cyclic condensation products prepared from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino2,6-dichloro -1,3,5-triazine.

d) Cyasorb® UV 3346 (Cytec) means a compound of the formula 92.

e) Hostavin®N30 (Hoechst) means a reaction product of the compound of the formula

with epichlorohydrin (amine W).

f) Uvasorb®HA 88 (Sigma) means a compound of the formula 95.

FR R

N - (CH ^ - N (95) where R =

g) Uvinul®5050 (BASF) means a compound of the formula A '.

AT 406 583 B

h) Chimassorb® 119 FL / 10 (Ciba-Geigy) means a condensation product prepared from 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3, 5-triazine and 1,2-bis (3aminopropylamino) ethane.

Thereafter, pipes with a nominal outside diameter of 20 mm and a nominal wall thickness of 2 mm are produced using an extruder of the Maillefer type with the extrusion parameters listed in Table 11.

Table 11: Machine parameters for pipe production

Barrel temperatures nozzle temperatures screw geometry cooling medium take-off speed

185, 195, 210 and 220 ° C, 220, 200 and 190 ° CL / d = 25, d = 60 mm 56 rpm water 6 m / minute

The stabilized polyethylene pipes are tested at 105 ° C. (pipes inside water, outside air) and a comparison stress of 1.5 MPa in the internal creep test (DIN 53759). At this low equivalent stress, a polyolefin pipe fails solely through thermo-oxidative degradation of the polyolefin material. The longer the service life, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water or gas, which is in constant contact with the polyolefins. The results are in the table

12th summarized.

Table 12: Stability of pipes (inside water, outside air)

<td>Examples</td><td>Service life in hours at an equivalent stress of 1.5 MPa</td>

<td>Example 4a</td><td> 10005</td>

<td>Example 4b</td><td> 13245</td>

<td>Example 4c</td><td> 11968</td>

<td>Example 4d</td><td> 11902</td>

<td>Example 4e</td><td> 11858</td>

<td>Example 4f</td><td> 12012</td>

<td>Example 4g</td><td> 15521</td>

Example 5: Stability of polyethylene stabilized with a component (b) and a component (c) (iii) which is in permanent contact with water

In analogy to Example 1, the stabilizers shown in Table 13 are incorporated into the polyethylene of medium density (PE-LLD, MFI at 230 ° C. / 2.16 kg = 1.0 g / 10 minutes, density = 0.937 g / cm3) incorporated.

<td>Tabel</td><td colspan="4"> 3:</td>

<td>example</td><td>stabilizer</td><td>Amount (wt.%)</td><td>molar mass (g / mol)</td><td>M.p. (° C)</td>

<td>Example 5a</td><td>Irgafos 168a)Irganox MD1024b) Irganox 1330a)</td><td> 0,10 0,07 0,20</td><td> 647 553 775</td><td> 180-185 224-229 241-245</td>

<td>Example 5b</td><td>Irgafos 168a)Irganox MD1024b> Irganox 1330a) Chimassorb 944a)</td><td> 0,10 0,07 0,10 0,10</td><td> 647 553 775 2580</td><td> 180-185 224-229 241-245 100-125</td>

<td>Example 5c</td><td>Irgafos 168a)Irganox MD1024b) Irganox 1330a> Chimassorb 119 FL / 10a)</td><td> 0,10 0,07 0,10 0,10</td><td> 647 553 775 2580</td><td> 180-185 224-229 241-245 100-125</td>

a) The chemical structures of Irgafos®168, Irganox®1330, Chimassorb®944 and Chimassorb®119 FL / 10 are disclosed in Examples 1, 2, 3 or 4.

b) Irganox®MD 1024 (Ciba-Geigy) means a compound of the formula

(lrganox®MD 1024) (CHgfcjC

AT 406 583 B

In analogy to Example 1, the stabilized polyethylene test plates are exposed to the water extraction conditions described in Example 1 at 90 ° C. for 12 months. After the extraction tests have been completed, the test plates are subjected to oven aging in a convection oven at 110 ° C. and the time taken for the polyolefin material to become brittle is measured. The longer the time until embrittlement, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water, which is in constant contact with the polyolefins. The results are summarized in Table 14.

Table 14: Oven aging

<td>Examples</td><td>Time to embrittlement in days</td>

<td>Example 5a</td><td> 10</td>

<td>Example 5b</td><td> 1071</td>

<td>Example 5c</td><td> 1255</td>

Example 6: Stability of polypropylene stabilized with a component (b) and a component (c) (iii) which is in permanent contact with water.

In analogy to Example 1, the stabilizers shown in Table 15 are converted into the polypropylene rPP (statistical polypropylene copolymer, MFI at 230 ° C. / 2.16 kg = 0.8 g / 10 minutes, density = 0.910 g / cm3) incorporated.

Table 15: (continued)

<td>example</td><td>stabilizer</td><td>lot (Wt%)</td><td>molar mass (g / raol)</td><td>M.p. (° C)</td>

<td rowspan="2">Example 6a</td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Irganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 6b</td><td>Irganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Chimassorb 944a)</td><td> 0,10</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos 168a)</td><td> 0,10</td><td> 647</td><td> 180-185</td>

<td>Example 6c</td><td>Irganox 1076bi</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Cyasorb 3346a)</td><td> 0,10</td><td> 1500-1800</td><td> 110-130</td>

<td></td><td>Irgafos PEPQ®5</td><td> 0,10</td><td> 991</td><td> 85-110</td>

<td>Example 6d</td><td>Irganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Chimassorb 944a)</td><td> 0,10</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos PEPQ ^</td><td> 0,10</td><td> 991</td><td> 85-110</td>

<td>Example 6e</td><td>Irganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Cyasorb 3346 »)</td><td> 0,10</td><td> 1500-1800</td><td> 110-130</td>

<td></td><td>Irgafos 38 ^</td><td> 0,10</td><td> 514</td><td> 89-92</td>

<td>Example 6f</td><td>Irganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Chimassorb 944a)</td><td> 0,10</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos 38 ^</td><td> 0,10</td><td> 514</td><td> 89-92</td>

<td>Example 6g</td><td>Irganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Cyasorb 3346 *></td><td>5S 0.10</td><td> 1500-1800</td><td> 110-130</td>

AT 406 583 B

Table 15: (composition)

<td>example</td><td>stabilizer</td><td>lot (Wt%)</td><td>molar mass (g / mol)</td><td>M.p. (° C)</td>

<td></td><td>Irgafos 12 ”</td><td> 0,10</td><td> 1465</td><td> 205</td>

<td>Example 6h</td><td>Liganox 1076b)</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Chimassorb 944 ”</td><td> 0,10</td><td> 2580</td><td> 100-125</td>

<td></td><td>Irgafos 12®5</td><td> 0,10</td><td> 1465</td><td> 205</td>

<td>Example 6i</td><td>Iiganox 1076 ”</td><td> 0,05</td><td> 531</td><td> 50-55</td>

<td></td><td>Cyasorb 3346 ”</td><td> 0,10</td><td> 1500-1800</td><td> 110-130</td>

a) The chemical structures of Irgafos®168, Chimassorb®944 and Cyasorb®3346 are disclosed in Examples 1, 2, 3, 4 or 5.

b) Irganox®1076 (Ciba-Geigy) means a compound of the formula

(CH ^ C

O

II

CHjj-CHg — C — O - ^ 18 ^ 37 (Irganox®1076)

c) lrgafos®PEPQ (Ciba-Geigy) means a compound of the formula Ph-3.

C (CH3)3

d) lrgafos®38 (Ciba-Geigy) means a compound of the formula Ph-1.

(CH ^ C

CiCHgYes

C (CH3)3 (Ph-1)

e) Irgafos® 12 (Ciba-Geigy) means a compound of the formula Ph-11.

AT 406 583 B

• O-CHj; -CHgN (Ph-11)

In analogy to Example 1, the stabilized polypropylene test plates are exposed to the water extraction conditions described in Example 1 at 98 ° C. for 6 months. After the extraction tests have been completed, the test plates are subjected to oven aging in a convection oven at 135 ° C and the time taken for the polyolefin material to become brittle is measured. The longer the time until embrittlement, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water, which is in permanent contact with the polyolefins.

Table 16: Oven aging

<td>Examples</td><td>Time to embrittlement in days</td>

<td>Example 6a</td><td> 5</td>

<td>Example 6b</td><td> 33</td>

<td>Example 6c</td><td> 36</td>

<td>Example 6d</td><td> 32</td>

<td>Example 6e</td><td> 36</td>

<td>Example 6f</td><td> 38</td>

<td>Example 6g</td><td> 42</td>

<td>Example 6h</td><td> 35</td>

<td>Example 6i</td><td> 34</td>

Example 7: Stability of polypropylene stabilized with a component (b) and a component (c) (iii) which is in permanent contact with water

In analogy to Example 1, the stabilizers shown in Table 17 are incorporated into the polypropylene (MFI at 230 ° C. / 2.16 kg = 2.0 g / 10 minutes, density = 0.905 g / cm3) incorporated.

<td>Tabel</td><td colspan="4"> 7:</td>

<td>example</td><td>stabilizer</td><td>Amount (wt.%)</td><td>molar mass (g / mol)</td><td>M.p. (° C)</td>

<td>Example 7a</td><td>Irgafos 168a)Irganox 1010a)</td><td> 0,10 0,35</td><td> 647 1178</td><td> 180-185 110-125</td>

<td>Example 7b</td><td>Irgafos 168a)Irganox 1010a) Chimassorb 119 FL / 10a)</td><td> 0,10 0,05 0,35</td><td> 647 1178 2580</td><td> 180-185 110-125 100-125</td>

a) The chemical structures of Irgafos®168, Irganox®1010 and Chimassorb® 119 FL / 10 are disclosed in Examples 1, 2, 3, 4, 5 or 6.

In analogy to Example 1, the stabilized polypropylene test plates are exposed to the water extraction conditions described in Example 1 at 98 ° C. for 12 months. After completion of the extraction tests, the test plates are subjected to oven aging in a convection oven at 120 ° C and the time taken for the polyolefin material to become brittle is measured. Ever

AT 406 583 B the longer the time until embrittlement, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water, which is in permanent contact with the polyolefins.

Table 18: Oven aging

<td>Examples</td><td>Time to embrittlement in days</td>

<td>Example 7a</td><td> 215</td>

<td>Example 7b</td><td> 504</td>

Patent claims:

Contents74

Every citation, both ways

Citations
Document	Relation	Office	Cited during
EP0184191A2	Cites	European Patent Office (EPO)	Search report
EP0324106A1	Cites	European Patent Office (EPO)	Search report
EP0359276A2	Cites	European Patent Office (EPO)	Search report
EP0391438A2	Cites	European Patent Office (EPO)	Search report
EP0427674A1	Cites	European Patent Office (EPO)	Search report
EP0553498A2	Cites	European Patent Office (EPO)	Search report
EP0635514A1	Cites	European Patent Office (EPO)	Search report
US4532165A	Cites	United States of America	Search report
JPH01103638A	Cites	Japan	Search report

32 members in 17 offices

This recordMember, by publication datePriority claim7 more offices are in the list below

Priority claims5

Priority claims
Document	Office	Kind	Date
261695	Switzerland	A	1995-09-15
70997596	United States of America	A	1996-09-09
261695	–	–	–
CH19950002616	–	–	–
US19960709975	–	–	–

Members32

Family members, oldest first
Document	Office	Kind
SE9603317D0	Sweden	D0	1996-09-12
FI963613A0	Finland	A0	1996-09-13
NO963830D0	Norway	D0	1996-09-13
CA2185488A1	Canada	A1	1997-03-16
FI963613A	Finland	A	1997-03-16
FI963613L	Finland	L	1997-03-16
SE9603317L	Sweden	L	1997-03-16
NO963830L	Norway	L	1997-03-17
DE19637181A1	Germany	A1	1997-03-20
NL1004035A1	Netherlands (Kingdom of the)	A1	1997-03-20
FR2738834A1	France	A1	1997-03-21
GB2305180A	United Kingdom	A	1997-04-02
JPH09111056A	Japan	A	1997-04-28
KR970015652A	Republic of Korea	A	1997-04-28
ITMI961874A1	Italy	A1	1998-03-12
NL1004035C2	Netherlands (Kingdom of the)	C2	1998-03-17
IT1284515B1	Italy	B1	1998-05-21
BR9603752A	Brazil	A	1998-06-02
BE1010623A5	Belgium	A5	1998-11-03
FR2738834B1	France	B1	1998-11-27
SE509371C2	Sweden	C2	1999-01-18
ATA161796A	Austria	A	1999-11-15
ES2137823A1	Spain	A1	1999-12-16
AT406583BThis record	Austria	B	2000-06-26
ES2137823B1	Spain	B1	2000-08-16
TW438850B	Taiwan Province of China	B	2001-06-07
US6541547B1	United States of America	B1	2003-04-01
KR100449438B1	Republic of Korea	B1	2005-04-06
NO323258B1	Norway	B1	2007-02-19
DE19637181B4	Germany	B4	2007-11-15
FI118737B	Finland	B	2008-02-29
CA2185488C	Canada	C	2009-03-24

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	Event	Code
2016-11-15	ExpiryMK07	MK07
1998-08-15	Publication of translation of european patent specificationUEP	UEP