CA2185488C

Stabilization of polyolefins in permanent contact with extracting media

Abstract

Polyolefin mouldings which have excellent stability on permanent contact with extracting media comprise, as stabilizers, a selected mixture comprising an organic phosphite or phosphonite and a specially selected group of sterically hindered phenols or a certain group of sterically hindered amines. In addition, a selected three-component mixture comprising a phosphite or phosphonite, a phenolic antioxidant and a certain group of sterically hindered amines is particularly suitable as stabilizer for polyolefin mouldings which are in permanent contact with extracting media.

CA2185488C, drawing sheet 1 — Sheet 1 of 141

Term

Term ended

Expired 13 September 2016, 10 years ago.

3 claims: 1 independent, 2 dependent

1
CA 02185488 2007-12-12 29276-401 - 89CLAIMS :1. A process for stabilizing a thick-walled polyolefin moulding which is in permanent contact with water, which comprises incorporating in or applying to said moulding a mixture of a component (bj in an amount of from 0.02 to 0.6 % based on the weight of the moulding, a component (c) in an amount of from 0.02 to 0.5 % based on the weight of the moulding ' id a component (d) in an amount of from 0.02 to 1.0 % based on the weight of the moulding, in which component (b) is tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butyl-6-methyl) C(CH 3 ) 3 C(CH 3 ) 3 (Ph-3) component (c) is a compound of the formula I CA 02185488 2007-05-23 29276-401 in which n is 3, R] and R 2 are tert-butyl, R 3 is hydrogen, and (CH 3 ) 3 C ch 2 - ch 2 O II cNHor (CH 3 ) 3 C CA 02185488 2007-05-23 29276-401 -91 component (d) is a compound from the group consisting of sterically hindered amines in which the molecular weight is greater than 1000 and the compound contains at least one radical of the formula VI or VI’ in which R 13 is hydrogen or methyl. CA 02185488 2007-12-12 29276-401 -922. A process according to claim 1, wherein the mixture of components (b), (c) and (d) comprises further additives .

1,072 paragraphs in 52 sections, as filed

A-20564/A

Stabilization of polyolefins in permanent contact with extracting media

The present invention relates to compositions comprising a polyolefin which is in permanent contact with extracting media, and stabilizer mixtures, to the use thereof for stabilizing thick-layer polyolefin mouldings, and to a process for stabilizing thick-layer polyolefin mouldings.

R. Gachter and H. Miiller, Plastics Additives Handbook, 3rd Edition, pages 1 to 100 (1990), discloses, for example, that polyolefins can be protected against oxidative damage during preparation, processing and use by means of suitable stabilizer mixtures. In many cases, the stabilized polyolefin mouldings are in contact with liquid or gaseous media during use. It is therefore necessary that the stabilizer mixtures added to the polyolefin moulding have adequate chemical resistance to the particular contact media. Examples of polyolefin mouldings which are particularly at risk are pipes, undersea cables, tanks and geomembranes which are in permanent contact with extracting media.

EP-A-0 324 106 describes a polyolefin moulding composition which has particularly good stability in permanent contact with extracting media. The stabilizer mixture used is a symmetrical triaryl phosphite and an ester of 3,3-bis(3’-tert-butyl-4’-hydroxyphenyl)butanoic acid.

It has now been found that a selected mixture comprising 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 mouldings which are in permanent contact with extracting media. It has also been found that a threecomponent mixture comprising a phosphite or phosphonite, a phenolic antioxidant and a certain group of sterically hindered amines is particularly suitable as stabilizer for polyolefin mouldings which are in permanent contact with extracting media.

The present invention therefore relates to compositions comprising

a) a polyolefin which is in permanent contact with extracting media,

b) at least one compound from the group consisting of organic phosphites or phosphonites,

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

in which n is the number 1 or 3,

R; is CpC^alkyl, C5-C12cycloalkyl, phenyl or C7-C9phenylalkyl,

R2 is hydrogen, C1-C18alkyl, C5-C12cycloalkyl, phenyl or C7-C9phenylalkyl, R3 is hydrogen or methyl, if n is 1,

O

R4 is hydrogen, CrC4alkyl or

if n is 3,

CH3-CH— ch2-ch I \ r5 is hydrogen or methyl,

R6 is hydrogen, CrC20alkyl, unsubstituted or CrC4alkyl-substituted phenyl or

Mr + naphthyl; or- , r

R7 is CrC20alkyl, unsubstituted or CrC4alkyl-substituted phenyl or naphthyl,

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

CA 02185488 2007-05-23

29276-401

G-H2C

CHgG,

N N\_7

-h2c^

CH, σν), in which

G is hydrogen or methyl,

G j and G2 are hydrogen, methyl or together are =0; or (iii) (x) at least one compound from the group consisting of phenolic antioxidants, and (y) at least one compound from the group consisting of sterically hindered amities having a molecular weight of greater than 500 and containing at least one radical of the formula ΠΙ or IV.

CA 02185488 2007-12-12

29276-401 ' jâAccording to one aspect of the present invention there is provided a process for stabilizing a thick-walled polyolefin moulding which is in permanent contact with water, which comprises incorporating in or applying to said moulding a mixture of a component (b) in an amount of from 0.02 to 0.6 % based on the weight of the moulding, a component (c) in an amount of from 0.02 to 0.5 % based on the weight of the moulding and a component (d) in an amount of from 0.02 to 1.0 % based on the weight of the moulding, in which component (b) is tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-buty]-6-methyl) ethyl phosphite or a compound of the formula Ph-3 or Ph-l 1

o — ch2— ch2N (Ph-11);

component (c) is a compound of the formula I

CA 02185488 2007-05-23

29276-401

-3b-

R (I) in which n is 3,

Rj and R2 are tert-butyl, R3 is hydrogen, and

CH,

Rx is

H3C

HnC

CH,

CH,

CH, ch2 or 0^Ν^0

I j ; or in which component (c) is

CH2CH2-C-O-CH2 (CH3)3C

CH2-CH2-C — NHo

II or

(CH3)3C

CH2 CH2 C O rï-C-|gH37 ; and

CA 02185488 2007-05-23

29276-401

-3ccomponent (d) is a compound from the group consisting of sterically hindered amines in which the molecular weight is greater than 1000 and the compound contains at least one radical of the formula VI or VI’

in which

Rj3 is hydrogen or methyl.

Alkyl having up to 20 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbuty], n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,

1,1,3-trimethylhexyl, 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. R] and R2 are preferably Cj-C^alkyl, in particular CrC8alkyl, for example tert-butyl. R7 is particularly preferably Cj-C^alkyl, in particular CrC]OaJkyl, for example Cj-Cgalkyl.

Excluded from the compounds that can make up component b) is tris[2-tert-butyl-4-(2methyl-4-hydroxy-5-tert-butylphenylthio)-5-methyl]-phenyl phosphite.

In the composition of the invention, there is a proviso: if component (a) is poly-1-butene and component (c)(i) is l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6trimethylbenzene, component (b) is not tris(2,4-di-tert-butyl-phenyl)phosphite.

CA 02185488 2007-05-23

29276-401

-3dC5-C12cycloalkyl, in particular C5-Cgcycloalkyl, is, for example, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclohexyl is preferred.

C7-C9phenylalkyl is, for example, benzyl, a-methylbenzyl, α,α-dimethylbenzyl or 2-phenylethyl.

Cj-C^alkyl-substituted phenyl or naphthyl, which preferably contains 1 to 3, in particular 1 or 2, alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-di methylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-iert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl or

-44-tert-butylnaphthyl.

A monovalent, divalent or trivalent metal cation is preferably a cation of an alkali metal, alkaline earth metal, heavy metal or aluminium, for example Na+, K+, Mg++, Ca++, Ba++, Zn++ or Al+++. Ca++ is particularly preferred.

Of interest are compositions in which component (b) is an organic phosphite or phosphorite of the formula (1) to (7)

in which the indices are integers and ri is 2, 3 or 4; p is 1 or 2; q is 2 or 3; r is 4 to 12; y is 1, 2 or 3; and z is 1 to 6;

A’, if ri is 2, is alkylene having 2 to 18 carbon atoms; alkylene having 2 to 12 carbon

-5atoms which is interrupted by -S-, -O- or -NR’4-; a radical of the formula

or phenylene;

A’, if n’ is 3, is a radical of the formula -C^H2r-i'i

A', if n' is 4, is tbe radical of the formula C(CH^“ ;

A is as defined for A’ if n’ is 2;

B’ is a radical of the formula -CH2-; -CHR4-; -CR^R^-; -S- or a direct bond; or C5-C7cycloalkylidene; or cyclohexylidene which is substituted by 1 to 4 Cp^alkyl radicals in position 3,4 and/or 5;

D’, if p is 1, is methyl and, if p is 2, is -CH2OCH2-;

E’, if y is 1, is alkyl having 1 to 18 carbon atoms, a radical of the formula -OR’! or halogen;

E’, if y is 2, is a radical of the formula -0-A-0-;

E’, if y is 3, is a radical of the formula R^QCl^O-)^-;

Q’ is the radical of an at least z-valent alcohol or phenol, this radical being bonded to the P atom(s) via the alcoholic or phenolic 0 atom(s);

R*!, R’2 and R’3, independently of one another, are alkyl having 1 to 30 carbon atoms; alkyl having 1 to 18 carbon atoms which is substituted by halogen, -COOR’4, -CN or -CONR’4R’4; alkyl having 2 to 18 carbon atoms which is interrupted by -S-, -0- or -NR’4-; phenyl-Cj-C4-alkyl; cycloalkyl having 5 to 12 carbon atoms; phenyl or naphthyl; phenyl or naphthyl which is substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms or phenyl-CpQalkyl; or a radical of the formula 0H , in which m is an integer in the range from 3 to 6;

each R’4, independently of the others, is hydrogen; alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms; or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety;

R’5 and R’6, independently of one another, are hydrogen; alkyl having 1 to 8 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;

R’7 and R’8, in the case where q = 2, are, independently of one another, CrC4alkyl or

-6together are a 2,3-dehydropentamethylene radical; and

R’7 and R’8, in the case where q = 3, are methyl;

the substituents R’14, independently of one another, are hydrogen; alkyl having 1 to 9 carbon atoms or cyclohexyl;

the substituents R’15, independently of one another, are hydrogen or methyl; and R’16 is hydrogen or CrC4alkyl, and in the case where a plurality of radicals R’16 are present, the radicals R’16 are identical or different;

X’ and Y’ are each a direct bond or -O-; and

Z’ is a direct bond; -CH2-; -C(R'16)2- or -S-.

Of particular interest are compositions comprising as component (b) a phosphite or phosphorite of the formula (1), (2), (5) or (6) in which ri is the number 2 and y is the number 1 or 2;

A’ is alkylene having 2 to 18 carbon atoms; p-phenylene or p-biphenylene;

E’, in the case where y = 1, is CrC18alkyl, -(^ or fluorine; and in the case where y = 2, is p-biphenylene;

R\, R’2 and R'3, independently of one another, are alkyl having 1 to 18 carbon atoms; phenyl-C^-Qalkyl; cyclohexyl; phenyl; or phenyl which is substituted by 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms;

the substituents R’14 independently of one another, are hydrogen or alkyl having 1 to 9 carbon atoms;

R’15 is hydrogen or methyl;

X’ is a direct bond;

Y’ is -O-; and

Z’ is a direct bond or -CH(R’16)-.

Also of interest are compositions comprising as component (b) a phosphite or phosphorite of the formula (1), (2), (5) or (6) in which ri is the number 2 and y is the number 1;

A’ is p-biphenylene;

E’ is CrC18alkoxy or fluorine;

R’j, R’2 and R’3, independently of one another, are alkyl having 1 to 18 carbon atoms; or phenyl which is substituted by 2 or 3 alkyl radicals having a total of 2 to 12 carbon atoms; the substituents R’14, independently of one another, are methyl or tert-butyl;

R’j5 is hydrogen;

X’ is a direct bond;

-7Y’ is -0-; and

Z’ is a direct bond, -CH2- or -CH(CH3)-.

Particular preference is given to compositions comprising as component (b) a phosphite, in particular of the formula (1) or (5).

The following compounds are examples of phosphites or phosphorites which are particu larly suitable as component (b) in the novel composition:

(CH3)3C

C(CH3)3 (Ph-1);

C(CH3)3

C(CH3)3 (Ph-2);

C(CH3)3 (CH3)3C (Ph-3);

(CH3)3C

C(CH3)3 (Ph-4);

C(CH3)3 (Ph-5);

(Ph-6);

(CH3)3C (Ph-7);

(CH3)3C (Ph-8);

(CH3)3C (Ph-9);

/θ —\ /— θ\

H37Ci8- Ο-pz Y V-o-c18h37

Ο — ' ο (Ph-10);

(Ph-11).

These phosphites and phosphorites are known compounds, and some are commercially available.

Particular preference is given to compositions comprising as component (b) a compound of the formula V, Ph-1, Ph-3 or Ph-11

O--P (V)

- 10(CH3)3C

C(CH3)3 (Ph-1)

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

CH,

CH, •N (Ph-11) in which

R9 and R12, independently of one another, are hydrogen, CrC8alkyl, cyclohexyl or phenyl, and

R10 and Rn, independently of one another, are hydrogen or C1-C4alkyl.

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

R! is CrC12alkyl, C5-C8cycloalkyl, phenyl or benzyl,

R2 is hydrogen, CrC12alkyl, C5-C8cycloalkyl, phenyl or benzyl,

- 11 R3 is hydrogen or methyl, if n is 1, ί /R*

R4is —CH2-P —O °-r7 if n is 3,

R5 is hydrogen or methyl,

Mr +

R6 is hydrogen, CrC12alkyl orr

R7 is Cx-C^alkyl,

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

Preference is given to compositions comprising as component (c)(i) a compound of the formula I in which n is the number 1 or 3,

R] is tert-butyl, cyclohexyl or phenyl,

R2 is hydrogen, tert-butyl, cyclohexyl or phenyl,

R3 is hydrogen, if nis 1, i?

R4is -CH2-P-0 t CL if n is 3,

R6 is C1-C4alkyl orr

R7 is CrC12alkyl,

Mr+ is calcium, and r is 2.

Very particular preference is given to compositions comprising as component (c)(i) a compound of the formula

OH

Irganox® 1330 (Ciba-Geigy)

Irganox® 3114 (Ciba-Geigy)

Irganox® 1222 (Ciba-Geigy)

Irganox® 1425 (Ciba-Geigy)

Of particular interest are compositions comprising as component (c)(ii) or component (c)(iii)(y) a sterically hindered amine from the class of compounds described under (a’) to (g’) which contain at least one radical of the formula ΠΙ or IV.

(a’) Compounds of the formula IV’

O--G (IV’)

-14in which n is a number from 1 to 4, G and G1 independently of one another, are hydrogen or methyl,

G11 is hydrogen, oxygen, hydroxyl, Cj-C^alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C12aralkyl, CrC18alkoxy, C5-C8cycloalkoxy, C7-C9phenylalkoxy, CrC8alkanoyl, C3-C5alkenoyl, CrC18alkanoyloxy, benzyloxy, glycidyl or a group of the formula -CH2CH(OH)-Z, in which Z is hydrogen, methyl or phenyl, G11 preferably being H, C1-C4alkyl, allyl, benzyl, acetyl or acryloyl, and

G12, if n is 1, is hydrogen, CpC^alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical or an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, or an α,β-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ12 groups, in which Z12 is H, CrC20alkyl, C3-C12alkenyl, C5-C7cycloalkyl, phenyl or benzyl,

G12, if n is 2, is C2-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical or an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ12 groups,

G12, if n is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZ12, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, and G12, if n is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

The carboxylic acid radicals mentioned above are in each case taken to mean radicals of the formula (-CO)nR, where n is as defined above, and the meaning of R arises from the definition given.

-15Any CrC12alkyl substituents are, 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.

CrC18alkyl G11 or G12 can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

C3-C8alkenyl G11 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.

C3-C8alkynyl G11 is preferably propargyl.

C7-C12aralkyl G11 is, in particular, phenethyl, especially benzyl.

CrC8alkanoyl G11 is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and C3-C5alkenoyl G11 is in particular acryloyl.

If G12 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If G12 is a monovalent silyl radical, it is, for example, a radical of the formula -(CjH2j)-Si(Z’)2Z, in which j is an integer in the range from 2 to 5, and Z’ and Z, independently of one another, are CrC4alkyl or CrC4alkoxy.

If G12 is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical.

If G12 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.

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

-16If G12 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

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 having 4-12 carbon atoms.

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

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

2) l-aUyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

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

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

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

6) l-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 6-(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

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

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

14) di(l,2,2,6,6-pentamethylpiperidin-4-yl) sebacate

15) di(l,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate

16) di(l-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

17) l-hydroxy-4-B-cyanoethoxy-2,2,6,6-tetramethylpiperidine

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

19) tri(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate

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

21) di(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate

22) di(l,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate

23) di( 1,2,2,6,6-pentamethylpiperidin-4-yl) butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate

24) di(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

25) di(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

26) hexane-1 ’ ,6’-bis(4-carbamoyloxy- l-n-butyl-2,2,6,6-tetramethylpiperidine)

- 1727) toluene-2’, 4’-bis-(4-carbamoyloxy-l-n-propyl-2,2,6,6-tetramethylpiperidine)

28) dimethylbis(2,2,6,6-tetramethylpiperidin-4-oxy)silane

29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane

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

31) tris(l-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate

32) phenyl bis(l,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) l-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine (b’) Compounds of the formula V’

.14 (V’) in which n is the number 1 or 2, G, G1 and G11 are as defined under (a’),

G13 is hydrogen, CpC^alkyl, C2-C5hydroxyalkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-C18alkanoyl, C3-C5alkenoyl, benzoyl or a group of the formula

GCH

G11 , CH3 r

Χχ

-N )GCH.

CH, and

G14, if n is 1, is hydrogen, CrC18alkyl, C3-C8alkenyl, C5-C7cycloalkyl, CrC4alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, in which Z is hydrogen, methyl or phenyl;

G14, if n is 2, is C2-C12alkylene, C6-C12arylene, xylylene, a -CH2-CH(OH)-CH2 group or a -CH2-CH(OH)-CH2-O-D-O- group, in which D is C2-C10alkylene, C6-C15arylene, C6-Ci2cycloalkylene, or, provided that G13 is not alkanoyl, alkenoyl or benzoyl, G14 can

-18altematively be l-oxo-C2-C12alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternatively the group -CO-, or, if n is 1, G13 and G14 together can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Any CrC12- or CrC18alkyl substituents are as defined above for (a’).

Any C5-C7cycloalkyl substituents are, in particular, cyclohexyl.

C7-C8aralkyl G13 is, in particular, phenylethyl or especially benzyl. C2-C5Hydroxyalkyl G13 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.

C2-C18alkanoyl G13 is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and C3-C5alkenoyl G13 is, in particular, acryloyl.

C2-C8alkenyl G14 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

G14 as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted CrC4alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

Any C2-C12alkylene substitutes are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Any C6-C15arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4’-diphenylene.

C6-C12cycloalkylene is, in particular cyclohexylene.

Preference is given to compounds of the formula V’ in which n is 1 or 2, G is hydrogen, G11 is hydrogen or methyl, G13 is hydrogen, CpC^alkyl or a group of the formula

and G14, in the case where n=l, is hydrogen or CrC12alkyl, and, in the case where n=2, is C2-C8alkylene or l-oxo-C2-Cgalkylene.

Examples of polyalkylpiperidine compounds from 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-diacetamide

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’-dibutyladipamide

42) N,N’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N’ -dicyclohexyl-2-hydroxypropylene1,3-diamine

43) N,N’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine

44) N,N’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)succinamide

45) di(2,2,6,6-tetramethylpiperidin-4-yl) N-(2,2,6,6-tetramethylpiperidin-4-yl)-Baminodipropionate

46) The compound of the formula

CH3-C-CH3

CH, CH3

CH3 — N ch3z ch3

N — CH2- CH(OH)- CH2— O I c4h9

-202185488

47) 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine

48) 4-(3-methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetramethylpiperidine

49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine (c’) Compounds of the formula VI’

(VF) in which n is the number 1 or 2, G, G1 and G11 are as defined under (a), and G15, if n is 1, is C2-C8alkylene, or C2-C8hydroxyalkylene or C4-C22acyloxyalkylene, and if n is 2, G15 is the (-CH2)2C(CH2-)2 group.

C2-C8alkylene or C2-C8hydroxyalkylene G15 is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.

C4-C22acyloxyalkylene G15 is, for example, 2-ethyl-2-acetoxymethylpropylene.

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

50) 9-aza-8,8,10,10-tetramethyl-l,5-dioxaspiro[5.5]undecane

51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-l,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-l,5-dioxaspiro[5.5]undecane

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

55) 2,2,6,6-tetramethylpiperidine-4-spiro-2’ -( 1 ’ ,3’ -dioxane)-5 ’ -spiro-5 -( 1 ,3 dioxane)-2-spiro-4’-(2’,2’,6’,6’-tetramethylpiperidine);

(d’) Compounds of the formulae VHA, VIIB and VIIC, preference being given to compounds of the formula VIIC,

(VIIA) (VIIB)

(VHC) in which n is the number 1 or 2, G, G1 and G11 are as defined under (a’),

G16 is hydrogen, CrC12alkyl, allyl, benzyl, glycidyl or C2-C6alkoxyalkyl, and G17, if n is 1, is hydrogen, Cj-C^alkyl, C3-C5alkenyl, C7-C9aralkyl, C5-C7cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C10aryl, glycidyl or a group of the formula -(CH2)p-COO-Q or of the formula -(CH2)p-O-CO-Q, in which p is 1 or 2, and Q is CrC4alkyl or phenyl, and G17, if n is 2, is C2-C12alkylene, C4-C12alkenylene, C6-C12arylene, a group of the formula -CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2-, in which D is C2-C10alkylene, C6-C15arylene, C6-C12cycloalkylene or a group of the formula -CH2CH(OZ’)CH2-(OCH2-CH(OZ’)CH2)2-, in which Z’ is hydrogen, CrC18alkyl, allyl, benzyl, C2-C12alkanoyl or benzoyl,

T! and T2, independently of one another, are hydrogen, CrC18alkyl or unsubstituted or halogen- or C1-C4alkyl-substituted C6-C10aryl or C7-C9aralkyl, or

Tj and T2 together with the carbon atom bonding them form a C5-C14cycloalkane ring.

Any CrC12alkyl substituents are, 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.

Any CrC18alkyl substituents can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

-22Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tertbutoxyethyl, isopropoxyethyl or propoxypropyl.

C3-C5alkenyl G17 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

C7-C9aralkyl G17, Tj and T2 are, in particular, phenethyl or especially benzyl. If T} and T2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

C2-C4hydroxyalkyl G17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C6-C10aryl G17, T1 and T2 are, in particular, phenyl or a- or β-naphthyl, which are unsubstituted or substituted by halogen or CrC4alkyl.

C2-C12alkylene G17 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C4-C12alkenylene G17 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.

C6-C12arylene G17 is, for example, 0-, m- or p-phenylene, 1,4-naphthylene or 4,4’-diphenylene.

C2-C12alkanoyl Z’ is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

C2-C10alkylene, C6-C15arylene or C6-C12cycloalkylene D is as defined under (b’).

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

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

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

58) 3-allyl-l,3,8-triaza-l,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) l,3,7,7,8,9,9-heptamethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione

-2361) 2-isopropyl-7,7,9,9-tetramethyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane

62) 2,2-dibutyl-7,7,9,9-tetramethyl-l-oxa-3,8-diaza-4-oxospiro[4.5]decane

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

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

65) 8-acetyl-3-dodecyl-l,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione and the compounds of the following formulae:

-242185488

- N-CHoCHoCOOC

-25(e’) Compounds of the formula ΥΠΓ, which are themselves preferred,

(VIIT) in which n is the number 1 or 2, and G18 is a group of the formula

~ G1 CH,

G2 7 i3.CH,G or — E—(A)—N N —G11 X \_J

ChkCH2G in which G and G11 are as defined under (a’), and G1 and G2 are hydrogen, methyl or, together, are a substituent =0,

E is -0- or -NG13-, A is C2-C6alkylene or -(CH2)3-O- and x is the number 0 or 1,

G13 is hydrogen, CrC12alkyl, C2-C5hydroxyalkyl or C5-C7cycloalkyl,

G19 is identical to G18 or is one of the groups -NG21G22, -OG23, -NHCH2OG23 or -N(CH2OG23)2,

G20, if n = 1, is identical to G18 or G19 and, if n = 2, is an -E-B-E- group, in which B is C2-C8alkylene or C2-C8alkylene which is interrupted by 1 or 2 -N(G21)- groups,

G21 is CrC12alkyl, cyclohexyl, benzyl or Cj-C^hydroxyalkyl or a group of the formula

G22 is CrC12alkyl, cyclohexyl, benzyl or CrC4hydroxyalkyl, and G23 is hydrogen,

CrC12alkyl or phenyl, or G21 and G22 together are C4-C5alkylene or C4-C5oxaalkylene, -CH2CH2 -ck2ch2 \ \ „ for example or a group of the formula ^Ν'θ ,

-CH2CH2

-26or G21 is a group of the formula

Any CrC12alkyl substituents are, 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.

Any C1-C4hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl,

3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C2-C6alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

If G21 and G22 together are C4-C5alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

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

(CH3CH2)2N

N(CH2CH3)2

70)

-2875)

76)

77) |H 3 R R CH

R-N-(CH2)3-f\|-(CH2)2-A-(CH2)3-N-F

-2978)

79) where R =

N-CH2CH2-OH

(f ) Oligomeric or polymeric compounds whose recurring structural unit contains a

2,2,6,6-tetraalkylpiperidinyl radical, in particular polyesters, polyethers, polyamides, poly amines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof which contain such radicals.

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

81)

82)

CH3 ch3

o o

II II ch2- ch2- O - C — (CH2)4— c 11 _/\ i-c-o -\.Nch7ch3

-31 83)

85)

86)

C4Hg

93) h3c h3c

94)

95) (CH2)6-N-CH2-CH2—j ch3 h3C ch3 h3c

IN

I

H

CH3

CH, i

H

branch in the __chain, m’ and m are each an integer in the range from 0-200, with the proviso that m’ + m = m.

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

O

-34with epichlorohydrin; polyesters made from butane-1,2,3,4-tetracarboxylic acid with a bifunctional alcohol of the formula

HO

CH, ''CH,— C — ·

CH

O—CH, CH,—O / \ /

CH, \ Cl?3 /°H c ch—c— ch;

/ \ / I ’

CH,

O—ch2 ch2—o whose carboxyl side chains originating from the tetracarboxylic acid has been esterified by means of 2,2,6,6-tetramethyl-4-hydroxypiperidine; compounds of the formula

CH, ;h2—c-ch2—CHI I

O=C o=c I I och3 or , in which approximately one third of the radicals R are

H3C CHa

-C2H5 and the others are

h3c ch3N ” H , and m is a number in the range from 2 to

200; or copolymers whose recurring unit is built up from 2 σCH,

C = CH2 units and 1 each of the units

N

C13H27

(g* ) Compounds of the formula X’

GCH2 CH3 o -, θ-Ν n — V__!

gch2 oh3 (X’) in which n is the number 1 or 2, G and G11 are as defined under (a’), and G14 is as defined

-35under (b’), but G14 cannot be -CONH-Z and -CH2-CH(OH)-CH2-O-D-O-.

Examples of such compounds are the following:

100)

101)

102)

CH3 CH3 q ch3 ch3

Λ-Χ

N-H

X/ > CH2—N NH - N —CH2 A (amine M) o 4 Yh3

CH, CH, ch3 ch3

CH, CH3 η

X/ J CH2-N N ch3 _n N— 4 0 CH3 ch3 ch3 ch3 ch3 ch3 o

CH3 _n C—ch2—/

N —CH,

Of interest are compositions comprising as component (c)(ii) or component (c)(iii)(y) a compound of the formula IV’ in which n is an integer in the range from 1 to 4, G and G1 are hydrogen, and

G11 is hydrogen or CpC^alkyl, and

G12, if n = 1 , is a radical of the formula -(CjH2j)-Si(Z’)2Z, in which j is an integer in the range from 2 to 5, and Z’ and Z, independently of one another, are CrC4alkyl or CrC4alkoxy, and

G12, ifn = 2, is a radical of an aliphatic dicarboxylic acid having 2 to 12 carbon atoms, which may be substituted by -COOZ12, where Z12 is CrC2oalkyl,

G12, ifn = 3, is a radical of an aromatic tricarboxylic acid having 9 to 15 carbon atoms, G12, ifn = 4, is a radical of an aliphatic tetracarboxylic acid having 8 to 12 carbon atoms; amines of particular industrial interest from this class are those of the formulae

(amine B),

(amine C), (amine D),

(amine E), and esters of butane-1,2,3,4-tetracarboxylic acid containing 2 l,2,2,6,6-pentamethyl-4hydroxypiperidine units and 2 C13H27-OH (amine F) units.

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

G11 is hydrogen or methyl,

G13 is hydrogen or CrC8alkyl, and

G14 is C2-Cgalkylene or l-oxo-C2-Cgalkylene; an amine of particular industrial interest from this class is the compound of the formula

(amine G);

compounds of the formula VIIC in which n is 1, G, G1 and G17 are hydrogen,

Gn is hydrogen or methyl, and

Tj and T2, together with the carbon atom bonding them, form a C5-C14cycloalkane ring; an amine of particular industrial interest from this class is the compound of the formula

(amine H);

compounds of the formula VIII’ in which n is 1 or 2, G18 and G19 are a group of the formula

CH, „ G1 CH3 G2 7 i3.CH, r

-E—CH V

N-G11 “Aru

CH, CH3 or

E—(A)—N

N-G'

CH,CH3

G11 is hydrogen or methyl,

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

E is -0- or -NG13-, A is C2-C6alkylene and x is the number 0 or 1

G13 is hydrogen, C1-C12alkyl or cyclohexyl,

G20, if n = 1, is identical to G18 and, if n = 2, is an -E-B-E- group, in which B is C2-C8alkylene or C2-C8alkylene which is interrupted by 1 or 2 -N(G21)- groups,

G21 is CrC12alkyl, cyclohexyl, benzyl or CrC4hydroxyalkyl or a group of the formula

-38or G21 is a group of the formula

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

(amines K and L);

compounds of the formula X’, in which n is 2, G11 is hydrogen or methyl and G14 is C2-C12alkylene;

an amine of particular industrial interest from this class is the above-described compound ( 100)(= amine M]; and oligomeric compounds containing 2 to 10 recurring units obtainable by reaction

-39CH3. >CH3 (i’) of G H > in which G24 is C2-C5hydroxyalkyl, with an aliphatic

CH3/XCH3

C2-C12dicar boxy lie acid or a suitable reactive derivate such as a diester, the dichloride or the anhydride;

(j’) of a linear oligomeric polyester made from a dialcohol and butane-1,2,3,4-tetracarboxylic acid with 2,2,6,6-tetramethyl-4-hydroxy-piperidine;

C2-C6alkylene, T3 is CrC18alkyl or cyclohexyl, T4 is hydrogen or CrC18alkyl, or T3 and T4 together are C4-C6alkylene or C3-C5oxaalkylene;

(Γ) of H2N-A-NH-A-NH2 with CH3

and

Br-A-Br, in which A is C2-C6alkylene;

CH CH, ^^2)9 GH3. / n3 1 1

V-^/O-C-CH, (m’) of compounds of the formula HN> with epichlorohydrin;

ΟΗ,Λίζ || o

and those of the formula

-402/85488 (O’) ch3

I ;h2— c —ch2— chi o=c

I

OCH,

O = C I

OR

-C2H5 and the others are , in which approximately one third of the radicals R are h3c ch.

N-H , and m is a number in the range from 2 to 10;

v .3 _-UCHa

H3C ch3 oligomeric amines of particular industrial interest also include those of the formulae (m is again a number in the range from 2 to 10)

-O-CH3 (CAS No. 65447-77-0; amine N);

m —ζ nch2-ch2-o-cch2-ch2c CH,

CH,

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

(amine Q);

CH,

I

-ch2— c-ch2— ch-0=C o=c i i och3 or

-41 (amine R), in which approximately one third of

H3C CH3 the radicals R are -C2H5 and the others are ; a linear polyester

N-H

H3C ch3 containing 2 to 10 recurring units made from butane-1,2,3,4-tetracarboxylic acid and a f3 ο-ch, ch2-o ch3 c

S—CH XC CH—C· ch3 o-ch^ ch—</ ch3 terminal groups and side chains are formed by esterification of the free carboxyl groups using 2,2,6,6-tetramethyl-4-hydroxypiperidine (amine S); a copolymer whose recurring CH,

ΗΟ^ Clj*3 /O-CH^CHj—CH3 oh dialcohol of the formula ch2—c—ch^ y; ch—c—ch^ , in which the Π3 0 unit is built up from 2 Ç 'ύ— C = CH2 units and 1

N

Ci3H27 unit and 1

unit (amine T);

the product of the reaction of H2N-(CH2)2-NH-(CH2)2-NH2 with

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

-42product of the reaction of the compound of the formula

with epichlorohydrin (amine W).

The oligomeric amines are frequently mixtures of compounds which differ from one another in chain length.

Of particular importance is the use of the above-specified amines A, B, C, D, E, F, G, H, J, K, L, M, N, O, P, Q, R, S, T, U, V and W.

For the novel compositions, particular preference is given to the addition of sterically hindered amines whose molecular weight or mean molecular weight Kîn is in the range from 500 to 10,000, in particular in the range from 1000 to 10,000. Of these, particular emphasis should again be made of sterically hindered amines whose molecular weight or mean molecular weight is in the range from 1500 to 10,000, for example in the range from 2000 to 7500.

Particular emphasis should be made of novel compositions in which component (c)(ii) or component (c)(iii)(y) consists of two or more compounds of the sterically hindered amine typeSpecial preference is given to compositions comprising as component (c)(ii) or component (c)(iii)(y) a compound from the group consisting of sterically hindered amines in which the molecular weight is greater than 1000 and the compound contains at least one radical of the formula VI or VI’

(VP) in which

-43R13 is hydrogen or methyl.

Very special preference is given to compositions comprising as component (c)(ii) or 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 contains at least one radical of the formula VI or VI’ and one radical of the formula VII

(VP)

(VH) in which

R13 is hydrogen or methyl.

Of very particular interest are compositions comprising as component (c)(ii) or 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-dichloro-1,3,5-triazine [Chimassorb® 944LD (Ciba-Geigy), amine P in the above description]; or a condensation product prepared from 2-chloro-4,6-di(4-n-butylamino-l,2,2,6,6-pentamethylpiperidyl)-l,3,5-triazine and l,2-bis(3-aminopropylamino)ethane [Chimassorb® 119FU10 (Ciba-Geigy), compound No. 76].

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

Of interest are compositions comprising as component (c)(iii)(x) a phenolic antioxidant of the formula IT

in which

A is hydrogen, CrC24alkyl, C5-C12cycloalkyl, phenyl-C1-C4alkyl, phenyl or a X

-CH2-S-R12or —θΗ2—group,

R —O7 D

D is CrC24alkyl, C5-C12cycloalkyl, phenyl-CrC4alkyl, phenyl or a -CH2-S-R12 group, X is hydrogen, CrC18alkyl or one of the -CaH2a-Sq-R13, -CbH2b-CO-OR14,

A

R is hydrogen or a group of the formula -C0-CH=CH2,

G* is hydrogen or C1-C12alkyl,

R12 is CrC18alkyl, phenyl or a -(CH2)c-CO-OR15 or -CH2CH2OR20 group,

A

R13 is hydrogen, C[-C18alkyl, phenyl, benzyl or a // \

OH

-(CH2)c-CO-OR15 or -CH2-CH2-OR20 group,

R14 is Cj-Cgoalkyl or one of the -CHR18-CH2-S-R19,

Ris ^16

Ri?

C2-C8alkylene, C4-C6thiaalkylene or a -CH2CH2(OCH2CH2)d- group, is C1-C24alkyl, is hydrogen, Q-C^alkyl or cyclohexyl, is Cj-Ci8alkyl, cyclohexyl, phenyl, Cj-C^alkyl-substituted phenyl or one of the A

]3 groups, or R16 and R17 together are

C4-C8alkylene, which may be interrupted by -O- or -NH-, R18 is hydrogen, CrC4alkyl or phenyl, R19 is CrC18alkyl, R20 is hydrogen, CrC24alkyl, phenyl, C2-C18alkanoyl or benzoyl, R21 is C1-C18alkyl, cyclohexyl, phenyl,

OH group,

-46R22 is hydrogen, CrC18alkyl, cyclohexyl, or a

group, or

R21 and R22 together are C4-C8alkylene, which may be interrupted by -O- or -NH-, R23 and R24 are -S-CrC18alkyl, a 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) is particularly preferably a compound of the formula IT in which is hydrogen, CrC8alkyl, cyclohexyl, phenyl or a -CH2-R23 or

group,

D is CrC8alkyl, cyclohexyl, phenyl or a -CH2-R24 group,

X is hydrogen, CrC8alkyl or one of the -CaH2a-Sq-R13, -CbH2b-CO-OR14,

Y

R24

-CH2N(R21)(R22),

R13 is CrC12alkyl, phenyl or a -(CH2)c-CO-OR15 group, A

R14 is CrC18alkyl or a -Q-O-CO-CbH2b0H group, in which Q is

C2-C8alkylene, -CH2-CH2-S-CH2CH2 or a -CH2CH2(OCH2CH2)d- group,

Rj5 is CrCl8alkyl,

R21 and R22, independently of one another, are hydrogen or CrC12alkyl or R21 and R22 together are C4-C8alkylene, which may be interrupted by -O- or -NH-,

-47a is 1 or 2, b is 1 or 2, c is 1 or 2, and d is 1, 2 or 3, and

R23 and R24 are -S-C1-C18alkyl.

Component (c)(iii)(x) is very particularly a compound of the formula IF in which

group,

D is hydrogen or CrC18alkyl,

X is hydrogen, C1-C4alkyl, -CH2-R23 or a group of the formula —ÿ \ \=<

'24 or

0H , and

R23 and R24 are -S-Ci-Ci8alkyl.

Component (c)(iii)(x) can also be a tocopherol or vitamin E derivative, for example a-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol or a mixture thereof. Preference is given to vitamin E itsef (a-tocopherol).

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

(H3C)3C

-48in which the mean molecular weight is from 600 to 700.

Particular preference is given to novel compositions comprising as component (c)(iii)(x) a compound of the formula VIII

in which

Ri is CpC^alkyl, C5-C12cycloalkyl, phenyl or C7-C9phenylalkyl,

R2 is hydrogen, CpC^alkyl, C5-C12cycloalkyl, phenyl or C7-C9phenylalkyl,

R3 is hydrogen or methyl, — CH2— CHQ is CmH2m or ' m14

R14 is CrC8alkyl,

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

R15 is C8-C20alkyl or C5-C12cycloalkyl, and if p is 2 and X is oxygen,

R15 is C2-C8alkylene or C4-C8alkylene which is interrupted by oxygen or sulfur; and if p is 2 and X is -NH-,

R15 is a direct bond, C2-C8alkylene or C4-C8alkylene which is interrupted by oxygen or sulfur; and if p is 4,

R15 is C4-C10alkanetetrayl.

Preferred compounds of the formula I or Π as component (c)(iii)(x) in the novel compositions are the same as for component (c)(i).

Especial preference is given to compositions comprising as component (c)(iii)(x) a compound of the formula I, II or VIII in which Rt and R2 are tert-butyl and m is 2.

-49Of very special interest are compositions comprising as component (c)(iii)(x) Irganox®1010 (Ciba-Geigy), Irganox®MD 1024 (Ciba-Geigy) and Irganox®1076 (Ciba-Geigy).

(CH3)3C

O

II

CH2CH2-C-O-CH2.

O ll

CH2-CH2—C — NH-c Irganox®1010 (Ciba-Geigy)

Irganox®MD 1024 (Ciba-Geigy)

HO—ç y—CH2-CH2—C—O—n-C18H37 Irganox®1076 (Ciba-Geigy)

Preference is furthermore given to compositions comprising as component (c) a component (i) or a component (iii).

Of very special interest are compositions comprising as 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

C(CH3)3 (CH3)3C

o—ch2—ch2N (Ph-11) as component (c)(i) a compound of the formula I in which n is 3,

Rj and R2 are tert-butyl,

R3 is hydrogen, and

as 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-octylamino2,6-dichloro-l,3,5-triazine; or a condensation product prepared from 2-chloro-4,6-di(4-nbutylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane; and

-51 as component (c)(iii)(x) is

(CH3)3C

O

II

CH2CH2-C-O-CH2.

CH2-CH2-C — NH-4 2 or (CH3)3C

CH2- CH2— C O — n-C,„H

18π37

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

Examples of polyolefins are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-l-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene; furthermore polyethylene (which can be crosslinked, if desired), for example high density polyethylene (HDPE), high density polyethylene of high molecular weight (HDPE-HMW), high density polyethylene of ultrahigh molecular weight (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 previous paragraph, in particular polyethylene and polypropylene, can be prepared by various processes, in particular by the following methods:

-52a) by means of free radicals (usually at high pressure and high temperature),

b) by means of a catalyst, where the catalyst usually contains one or more metals from group IVb, Vb, VIb or VIH. These metals usually contain one or more ligands, such as oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls and/or aryls, which can be either π- or σ-coordinated. These metal complexes can be free or fixed to supports, for example to activated magnesium chloride, titanium(IH) 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 further activators can be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, where the metals are elements from groups la, Ila and/or Ilia. The activators can have been modified, for example, by means of further ester, ether, amine or silyl ether groups. These catalyst systems are usually known as Phillips, Standard Oil Indiana, Ziegler(-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE,

PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene-but-l-ene, propylene-isobutylene, ethylene-but-l-ene, ethylene-hexene, ethylene-methylpentene, ethylene-heptene, ethylene-octene, propylene-butadiene, isobutylene-isoprene, ethylenealkyl acrylate, ethylene-alkyl methacrylate, ethylene-vinyl acetate copolymers or copolymers thereof with carbon monoxide or ethylene-acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidenenorbomene; as well as mixtures of such copolymers and their mixtures with polymers mentioned in 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 polyalkylene-carbon monoxide copolymers with an alternating or random structure, and mixtures thereof with other polymers, for example polyamides.

2!85488

-534. Hydrocarbon resins (for example C5-C9), including hydrogenated modifications thereof (for example tackifying resins) and mixtures of polyalkylenes and starch.

Preferred polyolefins are polyethylene, polypropylene and copolymers thereof with monoolefins and diolefins.

Particular mention should be made of the action of the stabilizer mixture comprising a component (b) and a component (c) against oxidative and thermal degradation of polyolefins, as occur during the processing of thermoplastics. The polyolefins stabilized in this way are in addition distinguished by excellent chemical resistance to extracting media with which they are in permanent contact.

Component (b) is preferably added to the polyolefin to be stabilized in an amount of from 0.02 to 0.6%, in particular from 0.05 to 0.2%, and component (c) is preferably added in an amount of from 0.02 to 1.0%, in particular from 0.05 to 0.3%, based on the weight of the polyolefin to be stabilized.

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

In addition to components (b) and (c), the novel compositions can comprise further costabilizers (additives), for example the following:

1, Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-ditert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditert-butyl-4-methoxymethylphenol, linear or side-chain-branched nonylphenols, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(r-methyl-undec-l'-yl)phenol, 2,4dimethyl-6-( 1 '-methylheptadec-1 '-yl)phenol, 2,4-dimethyl-6-( 1 '-methyltridec-1 '-yl)phenol and mixtures thereof.

-541.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 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 a-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2’-thiobis(6-tert-butyl4-methylphenol), 2,2’-thiobis(4-octylphenol), 4,4’-thiobis(6-tert-butyl-3-methylphenol), 4,4’-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidene bisphenols, for example 2,2’-methylenebis(6-tert-butyl-4-methylphenol), 2,2’-methylenebis(6-tert-butyl-4-ethylphenol), 2,2’-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2’-methylenebis(4-methyl-6-cyclohexylphenol), 2,2’-methylenebis(6-nonyl-4-methylphenol), 2,2’ -methylenebis(4,6-di-tert-butylphenol), 2,2’ -ethylidenebis(4,6-di-tert-butylphenol), 2,2’-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2’-methy lenebis[6-(a-methylbenzyl)-4-nonylphenol], 2,2’-methylenebis[6-(a,a-dimethylbenzyl)4-nonylphenol], 4,4’ -methylenebis(2,6-di-tert-butylphenol), 4,4’-methylenebis(6-tert-butyl-2-methylphenol), 1, l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy2-methylphenyl)butane, l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3’-tert-butyl-4’-hydroxyphenyl) butyrate], bis(3tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3’-tert-butyl-2’-hydroxy5’-methylbenzyl)-6-tert-butyl-4-methylphenyl] terephthalate, l,l-bis(3,5-dimethyl-2hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tertbutyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl4-hydroxy-2-methylphenyl)pentane.

-551.7. Ο-, Ν- and S-benzyl compounds, for example 3,5,3',5’-tetra-tert-butyl-4,4'-dihydroxy dibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3,5-ditert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

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

1.9. Hydroxybenzyl aromatic compounds, for example l,3,5-tris(3,5-di-tert-butyl-4hydroxybenzyl)-2,4,6-trimethylbenzene, l,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. Triazine compounds, for example 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4hydroxyanilino)-l,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-tri azine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di- tertbutyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-l,3,5-triazine, 1,3,5tris(3,5-di-tert-butyl-4-hydroxyphenyl-propionyl)hexahydro-l,3,5-triazine, l,3,5-tris(3,5dicyclohexyl-4-hydroxybenzyl)-isocyanurate.

1.11. Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tertbutyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of B-(3,5-di-tert-butyl-4-hydroxyphenvl)propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,

-56thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N’-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.14. Esters of B-(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, for example 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)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.15. Esters of B-(3,5-dicyclohexvl-4-hvdroxyphenyl)propionic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, 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)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- l-phospha-2,6,7-trioxabicyclo-[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butvl-4-hvdroxyphenylacetic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,

1.17. Amides of B-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid, for example N,N’-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N’-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N’-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl)hydrazine, N,N’-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxalamide.

1.18. Ascorbic acid (vitamin C).

1.19. Aminic antioxidants, for example N,N’-di-isopropyl-p-phenylenediamine, N,N’-di2185488

-57sec-butyl-p-phenylenediamine, N,N’-bis(l,4-dimethylpentyl)-p-phenylenediamine, N,N’bis(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N’-bis(l-methylheptyl)-p-phenylenediamine, N,N’ -dicyclohexyl-p-phenylenediamine, N,N’ -diphenyl-p-phenylenediamine, N,N’-di-(2-naphthyl)-p-phenylenediamine, N-isopropyl-N’-phenyl-p-phenylenediamine, N-( 1,3-dimethylbutyl)-N’ -phenyl-p-phenylenediamine, N-(l -methylheptyl)-N’ -phenyl-pphenylenediamine, N-cyclohexyl-N’-phenyl-p-phenylenediamine, 4-(p-toluenesulfonamido)diphenylamine, N,N’-dimethyl-N,N’-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-l-naphthylamine, N-(4-tert-octylphenyl)-l-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p’-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di-(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4’-diaminodiphenylmethane, 4,4’-diaminodiphenylmethane, Ν,Ν,Ν’,Ν’-tetramethyl4, 4’-diaminodiphenylmethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,2-di(phenylamino)propane, (o-tolyl)biguanide, di[4-(l’,3’-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-l-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/isohexyldiphenylamines, mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-l,4-benzothiazine, phenothiazine, mixture of monoand dialkylated tert-butyl/tert-octylphenothiazines, mixture of mono- and dialkylated tertoctylphenothiazines, N-allylphenothiazine, Ν,Ν,Ν’,Ν'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-ylhexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin4-ol.

2, UV absorbers and light stabilizers

2.1. 2-(2’ -HydroxyphenyDbenzotriazoles, for example 2-(2’-hydroxy-5’-methylphenyl)benzotriazole, 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-butyl-2’-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-4’-octoxyphenyl)benzotriazole, 2-(3’,5’-ditert-amyl-2’-hydroxyphenyl)benzotriazole, 2-(3’,5’-bis(a,a-dimethylbenzyl)-2’-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2’-hydroxy-5'-(2-octyloxycarbonylethyl)2185488

-58phenyl)-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-octyloxycarbonylethyl)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'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'methylenebis[4-( 1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl phenol] ; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)3-fc- where R = 3'-tert-butyl-4'hydroxy-5'-2H-benzotriazol-2-yl phenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2’,4’-trihydroxy and 2’-hydroxy-4,4’-dimethoxy derivatives.

2.3. Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl and isooctyl a-cyano-p,|3-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl and butyl a-cyano-p-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N-(p-carbomethoxy-p-cyanovinyl)-2methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2’-thiobis[4-(l,l,3,3-tetramethylbutyl)phenol], such as the 1:1 and 1:2 complexes, if desired with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as the methyl or ethyl esters, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl ketoxime, and nickel complexes of l-phenyl-4lauroyl-5-hydroxypyrazole, if desired with additional ligands.

2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethylpiperidin-4-yl) seba-592185488 cate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(l,2,2,6,6-pentamethylpiperidin4-yl) sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis( 1,2,2,6,6pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the product of the condensation of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the product of the condensation of N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-l,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4butanetetraoate, l,r-(l,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis( 1,2,2,6,6pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-noctyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione, bis(l-octyloxy-2,2,6,6tetramethylpiperidyl) sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, the product of the condensation of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l,3,5-triazine, the product of the condensation of 2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the product of the condensation of 2-chloro-4,6-di(4-nbutylamino-l,2,2,6,6-pentamethylpiperidyl)-l,3,5-triazine and l,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-l,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pynOlidine-2,5-dione, 3-dodecyl-l(l,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxyand 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the product of the condensation of N,N’bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-l,3,5-triazine, the product of the condensation of l,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-l,3,5-triazine, and âlso 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccin imide, N-(l,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9tetramethyi-l-oxa-3,8-diaza-4-oxospiro[4,5]decane, and the product of the reaction of

7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro [4,5]decane and epichlorohydrin.

2.7. Oxalamides, for example 4,4’-dioctyloxyoxanilide, 2,2’ diethoxyoxanilide, 2,2’-dioctyloxy-5,5’-di-tert-butyloxanilide, 2,2’-didodecyloxy-5,5’-di-tert-butyloxanilide, 2ethoxy-2’ -ethyloxanilide, N,N’ -bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tertbutyl-2’-ethyloxanilide and mixtures thereof with 2-ethoxy-2’-ethyl-5,4’-di-tert-butyloxanilide, and mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.

-602.8. 2-(2-Hydroxvphenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-l,3,5-triazine, 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, 2,4bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy4-octyloxyphenyl)-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-hydroxy-3-butoxypropoxy) phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5- triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)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)-l,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)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-(2hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

3. Metal deactivators, for example Ν,Ν’-diphenyloxalamide, N-salicylal-N’-salicyloylhydrazine, N,N’ -bis(salicyloyl)hydrazine, N,N’ -bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalodihydrazide, oxanilide, isophthalodihydrazide, sebacobisphenyl hydrazide, N,N’-diacetyladipodihydrazide, Ν,Ν’-bissalicyloyloxalodihydrazide and N,N’-bissalicyloylthiopropionodihydrazide.

4. Phosphites and phosphorites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythrityl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl diphosphite, bis-isodecyloxy pentaerythrityl diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythrityl diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythrityl diphosphite, tristearyl sorbityltriphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4’ -biphenylenediphosphonite,

6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-l,3,2-dioxaphosphocine, 6fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz[d,g]-l,3,2-dioxaphosphocine, bis(2,4-ditert-butyl-6-methylphenyl) methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.

-615. Hydroxylamines, for example Ν,Ν-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, Ν,Ν-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, Ν,Ν-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine made from hydrogenated tallow fatty amines.

6. Nitrones, for example N-benzyl-alpha-phenyl nitrone, N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecyl nitrone, Nhexadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecyl nitrone, nitrones derived from Ν,Ν-dialkylhydroxylamines prepared from hydrogenated tallow fatty amines.

7. Thiosynergists, for example dilauryl thiodipropionate and distearyl thiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide and pentaerythrityl tetrakis(p-dodecylmercapto)propionate.

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

10. Basic costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate and tin pyrocatecholate.

11. Nucleating agents, for example inorganic substances, 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 salts thereof, for example 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, for example ionic copolymers (ionomers).

-6212. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, sawdust and flours or fibres of other natural products, synthetic fibres.

Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow aids, optical brighteners, flameproofing agents, antistatic and blowing agents.

14. Benzofuranones and indolinones, as described, for example, 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-A-0 589 839 or EP-A-0 591 102, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)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)benzofuran-2-one, 3-(4acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one and 3-(3,5-dimethyl4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one.

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

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

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

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

Glass fibres as reinforcing agents are expediently added to the polyolefin in concentrations

-63of from 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 also comprise further additives, in particular UV absorbers and light stabilizers (point 2 in the list); amides of p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid (metal deactivators, point

1.17 in the list); nucleating agents (point 11 in the list) and/or fillers and reinforcing agents (point 12 in the list).

Of particular interest as additional additives are metal deactivators, for example Ν,Ν’-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine [Irganox ®MD 1024 (Ciba-Geigy)] or N,N’-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide [Naugard®XL-l (Uniroyal)].

Components (b) and (c) and any further additives used are incorporated into the polyolefin by known methods, for example before or during shaping or alternatively by applying the dissolved or dispersed stabilizer mixture to the polyolefin, if necessary 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 in which these components are present, in a concentration of from 2.5 to 25% by weight.

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

The stabilizer mixtures comprising 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) and (c), or mixtures thereof, can also be sprayed onto the polyolefin to be stabilized. They are capable of diluting other additives (for example the abovementioned conventional additives) or melts thereof, so that they can also be sprayed onto the polyolefin to be stabilized together with these additives. A particularly advantageous procedure is addition before spraying, during deactivation of the polymerization catalysts, in which case for example, the steam for deactivation can be used for the spraying.

In the case of polyolefins polymerized in spherical form, it may be advantageous, for example, to apply components (b) and (c), if desired together with other additives, by spraying.

-64The polyolefins stabilized in this way can be used in a wide variety of forms, in particular as thick-walled polyolefin mouldings, which are in permanent contact with extracting media, for example pipes for liquids or gases, sheeting, geomembranes, tapes, profiles or tanks.

The present invention also relates to a process for stabilizing thick-walled polyolefin mouldings which are in permanent contact with extracting media, which comprises incorporating or applying a mixture comprising a component (b) and a component (c) to these mouldings.

Preference is given to a process for stabilizing thick-walled polyolefin mouldings which are in permanent contact with extracting media in which the thick-walled polyolefin mouldings have a wall thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.

Also of particular interest is a process for stabilizing thick-walled polyolefin mouldings which are in permanent contact with extracting media, in which the thick-walled polyolefin mouldings are pipes or geomembranes.

The term geomembrane is taken to mean sheeting which is used, for example, in landfill sites and must have, for example, a life of up to 300 years.

Extracting media are, for example, liquid or gaseous inorganic or organic materials.

Examples of gaseous inorganic materials are oxygen; nitrogen; nitrogen oxides, for example NO, laughing gas or NO2; sulfur oxides, for example sulfur dioxide; halogens, for example fluorine or chlorine; Brônsted acids, for example hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid or hydrocyanic acid, or bases, for example ammonia.

Examples of gaseous organic materials are CrC4alkanes, for example methane, ethane, propane or butane; carbon monoxide; carbon dioxide; or phosgene.

Examples of liquid inorganic materials are water, chlorinated drinking water or aqueous saline solutions, for example sodium chloride solution (brine) or sodium sulfate solution;

-65bromine; acid halides, for example titanium tetrachloride, thionyl chloride, nitrosyl chloride or trimethylsilyl chloride; caustic lyes, for example aqueous sodium hydroxide (NaOH) solution, aqueous potassium hydroxide (KOH) solution, aqueous ammonia solution, aqueous sodium bicarbonate solution or aqueous soda solution.

Examples of liquid organic materials are organic solvents and liquid organic reagents.

Examples of organic solvents are aliphatic hydrocarbons, for example pentane, hexane, heptane, octane, gasoline, nonane or decane; alcohols, for example methanol, ethanol, isopropanol, butanol, pentanol, amyl alcohol, cyclohexanol, pentaerythritol, ethylene glycol, ethylene diglycol, methylcellosolve, polyethylene glycol or glycerol; ketones, for example acetone, diethyl ketone, methyl ethyl ketone, diphenyl ether or cyclohexanone; ethers, for example diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons, for example benzene, toluene or xylene; heterocyclic solvents, for example furan, pyridine, 2,6-lutidine or thiophene; dipolar aprotic solvents, for example dimethylformamide, diethylacetamide or acetonitrile; or surfactants.

Other extracting media according to the present invention are mixtures and solutions, in particular aqueous mixtures, emulsions or solutions, of liquid or gaseous inorganic and organic materials as listed above.

Of particular interest are extracting media which are of importance in the chemical industry or in landfill sites.

A preferred embodiment of the present invention is therefore the use of a mixture comprising a component (b) and a component (c) for stabilizing thick-walled polyolefin mouldings which are in permanent contact with extracting media.

The examples below illustrate the invention in greater detail. The parts and percentages are by weight.

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

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

-66Table 1: Material properties of the polyethylene at 23°C

<td> Property</td><td> Value</td><td> Unit</td><td> Test method</td>

<td> Density</td><td> 0.934</td><td> g/cm3</td><td> ISO 1872</td>

<td> Yield stress os</td><td> 18</td><td> N/mra2</td><td> ISO 6259</td>

<td> Elongation es</td><td> 9</td><td> %</td><td> ISO 6259</td>

<td> Elongation at break €r</td><td> >600</td><td> %</td><td> ISO 6259</td>

<td> Tangential modulus</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 softening point</td><td> 118</td><td> °C</td><td> ISO 306 A-50</td>

<td> Crystalline melting point</td><td> 123-127</td><td> °C</td><td> DSC</td>

0.1 % by weight of calcium stearate and the stabilizers listed in Table 2 are added in dry form to the polyethylene polymer removed directly from the reactor, and are incorporated for 2 minutes in a Pappenmaier mixer (type 20) (Examples la, lb and lc).

Table 2:

<td> Example</td><td> Stabilizer</td><td> Amount (%by weight)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td></td><td rowspan="2"> Irgafos 168a)</td><td> 0.1</td><td> 647</td><td> 180-185</td>

<td rowspan="2"> Example la</td><td rowspan="2"> 0.1</td><td rowspan="2"> 1178</td><td rowspan="2"> 110-125</td>

<td> Irganox 1010b)</td>

<td></td><td rowspan="2"> Irgafos 168a)</td><td> 0.1</td><td> 647</td><td> 180-185</td>

<td rowspan="2"> Example lb</td><td rowspan="2"> 0.1</td><td rowspan="2"> 775</td><td rowspan="2"> 241-245</td>

<td> Irganox 1330c)</td>

<td></td><td rowspan="2"> Irgafos 168a)</td><td> 0.1</td><td> 647</td><td> 180-185</td>

<td rowspan="2"> Example lc</td><td rowspan="2"> 0.1</td><td rowspan="2"> 784</td><td rowspan="2"> 218-223</td>

<td> Irganox 3114d)</td>

-67a) Irgafos® 168 (Ciba-Geigy) is tris(2,4-di-tert-butylphenyl) phosphite (formula Ph-2).

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

c) Irganox®1330 (Ciba-Geigy) is l,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6trimethylbenze.

d) Irganox®3114 (Ciba-Geigy) is 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate.

In an extruder from Dolci, Milan (screw geometry (L/D) = 35, screw speed 55 revolutions/minute, maximum die temperature 190°C, cooling of the feed zone), the stabilized polyolefin is homogenized and converted into about 60 kg of granules per formulation. For the extraction experiments in water, test sheets measuring 200 mm x 150 mm x 2 mm are pressed out of the granules of the individual formulations (Examples la, lb and lc) using the machine parameters laid down in Table 3

Table 3: Machine parameters for test sheets

<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>

by means of a bench press. In order to simplify demoulding of the test sheets, the pressing operation is carried out between two aluminium foils.

The stabilizer extraction experiments are carried out using deionized water. The extraction container is conditioned in a fan-assisted oven from Heraeus (Hanau, Germany) at a maximum temperature deviation of 1.5°C. For the extraction experiments below the boiling point of water, glass vessels are used. At a water temperature of 105°C, pressurized containers of stainless steel are used. Owing to the risk of oversaturation of the water with stabilizer, the amount of liquid for the experiments is set at about 400 ml for about 70 g of

-68polymer, and the water is replaced by fresh water at regular intervals, i.e. after each sample is taken.

The test sheets are exposed to the above-described experimental conditions for up to 16,032 hours (668 days). When the extraction experiments are complete, the oxidation temperature (Tox) of the test sheets is determined. The determination of the oxidation temperature is carried out by means of a DuPont 910 differential scanning calorimeter from TA Instruments (Alzenau, Germany) and using from 5 to 10 mg of sample and describes the commencement of thermal decomposition of the polyolefin sample in a dynamic experiment. These dynamic experiments are carried out in open aluminium crucibles at a heating rate of 10°C/min and at an initial temperature of 30°C in a normal atmosphere. For the temperature range up to 260°C, the calibration standard used is indium (melting point Ts = 156.8°C; enthalpy of melting AHS = 26.8 J/g). The higher the oxidation temperature (Tox), the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Tables 4 and 5.

Table 4: Extraction experiments in water at 95°C

<td rowspan="2"> Extraction duration (hours)</td><td colspan="3"> Oxidation temperature (Tox) in °C</td>

<td> Example la</td><td> Example lb</td><td> Example lc</td>

2485488

-69Table 5: Extraction experiments with water at 105°C

<td rowspan="2"> Extraction duration (hours)</td><td colspan="3"> Oxidation temperature (Tox) in °C</td>

<td> Example la</td><td> Example lb</td><td> Example lc</td>

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

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

Table 6:

<td> Example</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td> Example 2a</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 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>

a) Irgafos® 168 (Ciba-Geigy) is tris(2,4-di-tert-butylphenyl) phosphite.

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

c) Chimassorb®944LD (Ciba-Geigy) denotes the linear or cyclic condensation products prepared from N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-l,3,5-triazine.

d) Chimassorb® 119FI710 (Ciba-Geigy) denotes 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(3-aminopropylamino)ethane.

The stabilized polyethylene test sheets are subjected, analogously to Example 1, to the water extraction conditions described in Example 1 at 95°C for up to 16,030 hours (668 days). When the extraction experiments are complete, the tear strength in megapascals (MPa) of the test sheets is determined. The tear strength is measured in accordance with DIN 53504 using an S2 standard rod. The tensile tests are carried out at room temperature at the earliest 24 hours after the respective sample has been removed form the water bath. The take-off rate is 200 mm/minute. The higher the tear strength value, the better the poly olefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Table 7.

Table 7: Extraction experiments with water at 95°C

<td rowspan="2"> Extraction duration (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 which is in permanent contact with water and which has been stabilized by means of a component (b) and a component (c)(iii).

The stabilizers shown in Table 8 are incorporated into the medium-density polyethylene analogously to Example 1.

-71 Table 8:

<td> Example</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</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 1010b^</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 168a)</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 168a)</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 N30e)</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 1010b)</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 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

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

<td></td><td> Dastib 10828)</td><td> 0.20</td><td> 2970</td><td> 162-181</td>

<td></td><td> Irgafos 168a)</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 5050b)</td><td> 0.20</td><td> 3500</td><td> 95-125</td>

-72Table 8: (continuation)

<td> Example</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td></td><td> Irgafos 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

<td> Example 3h</td><td> Irganox 1010b)</td><td> 0.05</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 3i</td><td> Irganox 1010b)</td><td> 0.05</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 3j</td><td> Irganox 1010b) Uvasil 299k)</td><td> 0.05 0.20</td><td> 1178 1100-2500</td><td> 110-125</td>

<td></td><td> Irgafos 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

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

<td></td><td> Lichtschutzstoff UV-311)</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 31</td><td> Irganox 1010b)</td><td> 0.05</td><td> 1178</td><td> 110-125</td>

<td></td><td> Chimassorb 944m)</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 3m</td><td> Irganox 1010b)</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) is tris(2,4-di-tert-butylphenyl)phosphite.

-73Irganox® 1010 (Ciba-Geigy) is the pentaerythrol ester of 3-(3,5-di-tert-butyl-4 hydroxyphenylpropionic acid.

Tinuvin®622 (Ciba-Geigy) is poly-(N-p-hydroxyethyl-2,2,6,6-tetramethyl-4hydroxy-piperidyl succinate).

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

(92)

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

with epichlorohydrin (amin W).

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

H

-74g) Dastib® 1082 (Slovakia) is a compound of the formula 92’.

(92’)

h) Uvinul®5050 (BASF) is a compound of the formula A’.

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

(B’)

MARK®LA 68 (Asahi Denka) is a compound of the formula C’.

(C’)

Uvasil®299 (Great Lakes Chemicals) is a compound of the formula D’.

-761) Lichtschutzstoff UV-31 (Leuna) is a compound of the formula E’

in which R is octadecyl or 2,2,6,6-tetramethyl-4-piperidyl.

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

n) Chimassorb® 119FIV10 (Ciba-Geigy) denotes 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(3-aminopropylamino)ethane.

The stabilized polyethylene test sheets are subjected, analogously to Example 1, to the water extraction conditions described in Example 1 at 95°C for up to 16,030 hours (668 days). When the extraction experiments are complete, the tear strength of the test sheets is determined in percent The tear strength is measured in accordance with DIN 53504 using an S2 standard rod. The tensile tests are carried out at room temperature at the earliest 24 hours after the respective sample has been removed form the water bath. The take-off rate is 200 mm/minute. The higher the tear strength value, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Table 9.

-77Table 9: Extraction eperiments with water at 95°C

<td rowspan="2"> Examples</td><td colspan="5"> Tear strength in percent after x hours of extraction</td>

<td> Ohour</td><td> 2034 hours</td><td> 5708 hours</td><td> 7487 hours</td><td> 16030 hours</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 31</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 which is in permanent contact with water and which has been stabilized by means of a component (b) and a component (c)(iii).

The stabilizers shown in Table 10 are incorporated into the medium-density polyethylene analogously to Example 1.

-78Table 10:

<td> Example</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td> Example 4a</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 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 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

<td> Example 4d</td><td> Irganox 1010b)</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 1010b)</td><td> 0.05</td><td> 1178</td><td> 110-125</td>

<td></td><td> Hostavin Ν30^</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 5050g)</td><td> 0.20</td><td> 3500</td><td> 95-125</td>

-79Table 10: (continuation)

<td> Example</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td></td><td> Irgafos 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

<td> Example 4g</td><td> Irganox 1010b)</td><td> 0.05</td><td> 1178</td><td> 110-125</td>

<td></td><td> Chimassorb 119 FL/10h)</td><td> 0.20</td><td> 2580</td><td> 100-125</td>

a) Irgafos® 168 (Ciba-Geigy) is tris(2,4-di-tert-butylphenyl)phosphit.

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

c) Chimassorb®944(Ciba-Geigy) denotes the linear or cyclic condensation products pre pared from N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4tert-octylamino-2,6-dichloro-1,3,5-triazine.

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

(92)

e) Hostavin®N30 (Hoechst) is a reaction product of the compound the formula CHo CHfl ch2 -(CH2)9Ί3. I I

V O —C —CHo HO<

ch. ch3 II

I

C — NH with epichlorohydrin (amin W).

-80f) Uvasorb®HA 88 (Sigma) is a compound of the formula 95

1' ' 1

-(- N - (CH2)2— N - (CH2)2-^, in which R is

(95)

g) Uvinul®5050 (BASF) is a compound of the formula A’.

h) Chimassorb® 119 FI710 (Ciba-Geigy) denotes 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(3-aminopropylamino)ethane.

The polyethylene was extruded by an extruder of the Maillefer type to form pipes with an outside diameter of 20 mm and a wall-thickness of 2 mm. The machine parameters for the preparation of the pipes are summarized in Table 11.

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Table 11: Machine parameters for the prapartion of pipes

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<td> Cylinder temperature</td><td> 185, 195, 210 und 220°C</td>

<td> Nozzle temperature</td><td> 220,200 und 190°C</td>

<td> Screw configuration</td><td> L/d = 25, d = 60 mm</td>

<td> Screw speed</td><td> 56 rpm</td>

<td> Cooling agent</td><td> Water</td>

<td> Take-off speed</td><td> 6 m/minute</td>

The stability of the polyethylene pipes are measured at 105°C (inside of the pipe is water, outside of the pipe is air) and a hoop stress of 1.5 MPa in the inside compressive creep test according to DIN 53759. Under this low hoop stress a polyethylene pipe is decomposed by thermal-oxidative degradation. The higher the retention time value, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Table 12.

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

<td> Examples</td><td> Retention time in hours at a hoop 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>

Example5: Stability of polyethylene which is in permanent contact with water and which has been stabilized by means of a component (b) and a component (c)(iii).

-82The stabilizers shown in Table 13 are incorporated into the medium-density polyethylene (PE-LLD, MFI at 230°C/2.16 kg = 1.0 g/10 minutes, density = 0.937 g/cm3) analogously to Example 1.

Table 13:

<td> Example</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td></td><td> Irgafos 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

<td> Example 5a</td><td> Irganox MD1024b></td><td> 0.07</td><td> 553</td><td> 224-229</td>

<td></td><td> Irganox 1330a)</td><td> 0.20</td><td> 775</td><td> 241-245</td>

<td></td><td> Irgafos 168a)</td><td> 0.10</td><td> 647</td><td> 180-185</td>

<td rowspan="2"> Example 5b</td><td rowspan="2"> Irganox MD1024b) Irganox 1330a)</td><td> 0.07</td><td> 553</td><td> 224-229</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 rowspan="2"> Example 5c</td><td rowspan="2"> Irganox MD 1024b) Irganox 1330a)</td><td> 0.07</td><td> 553</td><td> 224-229</td>

<td></td><td> Chimassorb 119 FL/10a)</td><td> 0.10</td><td> 2580</td><td> 100-125</td>

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

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

CA 02185488 2007-05-23

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(Irganox®MD 1024)

The stabilized polyethylene test sheets are subjected, analogously to Example 1, to the water extraction conditions described in Example 1 at 90°C for up to 12 months. When the extraction experiments are complete, the sheets are subjected to an oven aging in a circulating air oven at 110°C. The time until the polyolefins are embrittled is measured. The higher time until the polyolefins are embrittled, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Table 14.

Table 14: Oven ageing

<td> Examples</td><td> Time until 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 which is in permanent contact with water and which has been stabilized by means of a component (b) and a component (c)(iii).

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

-84Table 15:

<td> Examples</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td> Example 6a</td><td> Irgafos 168a) Irganox 1076b)</td><td> 0.10 0.05</td><td> 647 531</td><td> 180-185 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 1076b)</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 PEPQ0)</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 PEPQ0)</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 3346a)</td><td> 0,10</td><td> 1500-1800</td><td> 110-130</td>

<td></td><td> Irgafos 38d)</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 38d)</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 3346a)</td><td> 0.10</td><td> 1500-1800</td><td> 110-130</td>

-85Table 15: (continuation)

<td> Examples</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td></td><td> Irgafos 12e)</td><td> 0.10</td><td> 1465</td><td> 205</td>

<td> Example 6h</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 12e)</td><td> 0.10</td><td> 1465</td><td> 205</td>

<td> Example 6i</td><td> Irganox 1076b)</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>

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

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

HO-Z CH2-CH2-C — O—n-C18H37 (Irganox®1076)

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

C(CH3)3 (CH3)3C

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

-86(CH3)3C

C(CH3)3 (Ph-1)

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

CH2-CH2(Ph-11)

The stabilized polypropylene test sheets are subjected, analogously to Example 1, to the water extraction conditions described in Example 1 at 98 °C for up to 6 months. When the extraction experiments are complete, the sheets are subjected to an oven aging in a circulating air oven at 135°C. The time until the polyolefins are embrittled is measured. The higher time until the polyolefins are embrittled, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Table 16.

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-87Table 16: Oven ageing

<td> Examples</td><td> Time until 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 which is in permanent contact with water and which has been stabilized by means of a component (b) and a component (c)(iii).

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) analogously to Example 1.

Table 17:

<td> Examples</td><td> Stabilizer</td><td> Amount (% by wt.)</td><td> Molar mass (g/mol)</td><td> m.p. (°C)</td>

<td> Example 7 a</td><td> Irgafos 168a) Irganox 1010a)</td><td> 0.10 0.35</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 7b</td><td> Irganox 1010a></td><td> 0.05</td><td> 1178</td><td> 110-125</td>

<td></td><td> Chimassorb 119 FL/10a)</td><td> 0.35</td><td> 2580</td><td> 100-125</td>

CA 02185488 2007-05-23

29276-401

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

The stabilized polypropylene test sheets are subjected, analogously to Example 1, to the water extraction conditions described in Example 1 at 98°C for up to 6 months. When the extraction experiments are complete, the sheets are subjected to an oven aging in a circulating air oven at 120°C. The time until the polyolefins are embrittled is measured. The higher time until the polyolefins are embrittled, the better the polyolefins are stabilized and the more stable the polyolefins are to extracting water which is in permanent contact with the polyolefins. The results are summarized in Table 18.

Table 18: Oven ageing

Examples Time until embrittlement in days Example 7a 215 Example 7b 504

32 members in 17 offices

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

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Priority claims
Document	Office	Kind	Date
261695	Switzerland	–	1995-09-15
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
AT406583B	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
CA2185488CThis record	Canada	C	2009-03-24

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	Event	Code
2016-11-15	ExpiryMKEX	MKEX
2003-09-10	Examination requestEEER	EEER

Abstract

Term

A-20564/A

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CA 02185488 2007-05-23

CA 02185488 2007-05-23

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CA 02185488 2007-05-23

Priority claims6

Members32

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