WO2004039877A2 - Stabilising agent mixture - Google Patents

Abstract

The invention relates to a stabilising agent mixture containing: (a) at least one compound of general formula (I), in which B represents a bridge -(R3) C=N- or -N=C(R3)-; R2 is identical to L' or a group -(R2N)C=C(L')2, whereby the two radicals R and L' respectively can be identical or different from one another; L' represents -CN, -COR, COOR, -SO2R; L represents oxygen, =NR or sulphur and R1, R3 and R represent independently of one another hydrogen, C1-C24 alkyl; C2-C24 alkenyl; C2-C24 alkynyl; C2-C8 alkoxyalkyl; optionally substituted C3-C12 cycloalkyl or C6-C20 aryl; an optionally substituted five- or six-membered heterocylic radical containing at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulphur; (b at least one compound selected from the group consisting of organic phosphites, organic phosphines and organic phosphonites; (c) optionally at least one compound selected from the group consisting of sterically hindered phenols; (d) optionally at least one compound selected from the group consisting of sterically hindered amines; (e) optionally at least one compound selected from the group of chromans; and (f) optionally at least one organic or inorganic salt selected from the group consisting of zinc salts, calcium salts, magnesium salts, cerium salts, iron salts and manganese salts. The invention also relates to non-living organic material, which contains an effective quantity of the inventive stabilising agent mixture, to objects, which are produced from materials stabilised in this manner, in addition to a method for stabilising non-living organic material against the negative influence of oxygen, heat and/or light, by adding an effective quantity of the inventive stabilising agent to the non-living organic material.

Description

stabilizer mixture

description

The present invention relates to a stabilizer mixture containing

(a) at least one compound of the general formula (I)

in what mean

B is a bridge - (R ³ ) C = N- or -N = C (R ³ ) -;

R ² is L 'or a group - (R ₂ N) C = C ('), where the two radicals R and L 'can each be the same or different from one another;

L 'is -CN, -COR, COOR, -S0R;

L is oxygen, = NR or sulfur; and

R ¹ , R ^{3 '} and R independently of one another hydrogen; linear or branched -CC ₂₄ alkyl; linear or branched C ₂ -C ₂₄ -alkenyl; linear or branched C ₂ -C ₂₄ alkynyl; linear or branched C -Cs alkoxyalkyl; optionally substituted C ₃ -C ₂ cycloalkyl; an optionally substituted, five- or six-membered heterocyclic radical which contains at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur; optionally substituted C ₆ -C ₂ o-aryl;

(b) at least one compound selected from the group consisting of organic phosphites, organic phosphines and organic phosphonites; (c) optionally at least one compound selected from the group consisting of sterically hindered phenols;

(d) optionally at least one compound selected from the group consisting of sterically hindered amines;

(e) optionally at least one compound selected from the group consisting of chromanes; and

(f) optionally at least one organic or inorganic salt selected from the group consisting of zinc, calcium, magnesium, cerium, iron and manganese salts.

The present invention further relates to non-living, organic material which contains an effective amount of the stabilizer mixture according to the invention, articles which have been produced from materials stabilized in this way, and a process for stabilizing non-living, organic material against the negative influence of Oxygen, heat and / or light by adding the stabilizer mixture according to the invention in an effective amount to the non-living organic material.

Japanese patent applications 50/155549 and 51/045151 describe the use of pyrazolone derivatives as stabilizers against the thermal degradation of ethylene and PVC polymers.

Organic phosphites, phosphines, phosphonites and phosphoramides are used as costabilizers, antioxidants and process stabilizers for organic materials, e.g. Polyolefins, known from the prior art. Examples of such connections can be found in the standard work R. Gächter / H. Müller (editor), "Plastic Additives Handbook" (1990), 31st edition, page 47, Verlag Hanser, Munich.

The patent US 4,360,617 describes stabilizer mixtures which contain symmetrical triaryl phosphites and phenolic antioxidants, and in particular the degradation of a wide variety of organic polymers induced by oxygen, heat and / or light, such as e.g. Counteract polyurethane, polyacrylonitrile, polyamide 12 or polystyrene.

Sterically hindered amines, especially those which carry 2,2,6,6-tetramethylpiperidine groups in the molecule, are known as "hindered amine light stabilizers"("HALS"). However, the stabilizers known hitherto are not able to solve all problems which are intended to be eliminated by the stabilizer or which in turn may arise from the stabilizer itself. Examples include storage stability, water absorption, sensitivity to hydrolysis, sufficient stabilization during polymer processing, color retention of the stabilized polymer, volatility of the stabilizer, migration of the stabilizer within the stabilized polymer, compatibility of the stabilizer with the polymer to be stabilized and improved light stability of the stabilized polymer , There is therefore a constant need for ever-improved stabilizers for organic polymers.

Accordingly, the stabilizer mixtures described at the outset were found which enable improved stabilization of the organic polymers added with them against their degradation induced by oxygen, heat and / or light.

Component (a) of the stabilizer mixtures according to the invention contains at least one compound of the general formula (I)

in what mean

B is a bridge - (R ³ ) C = N- or -N = C (R ³ ) -;

R ² is L 'or a group - (R ₂ N) C = C (L') ₂ where the two radicals R and L 'can each be the same or different;

L 'is -CN, -COR, COOR, -S0 ₂ R;

L is oxygen, = NR or sulfur; and

R ¹ , R ³ and R independently of one another are hydrogen; linear or branched -CC ₂₄ alkyl; linear or branched C -C ₄ alkenyl; linear or branched C ₂ -C ₄ alkynyl; linear or branched C ₂ -Cs alkoxyalkyl; optionally substituted C ₃ -C ₂ cycloalkyl; an optionally substituted, five or six-membered heterocyclic radical which contains at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur; optionally substituted C ₆ -C ₂₀ aryl.

The compounds of the formula (I) thus correspond to the compounds of the formulas (Ia) and (Ib) shown below

according to the invention also the tautomeric compounds (la ') and (Ib')

and (la ") and (Ib")

should be included.

The preparation of these compounds is known and is described, for example, in WO 95/04733. If the C ₃ -C ₂ cycloalkyl and C ₆ -C ₀ aryl groups as well as the five- or six-membered heterocyclic radicals are substituted, halogens such as chlorine or bromine, linear or branched C 1 -C ₄ -alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₂₄ alkynyl or C ₂ -C ₂₄ alkynyl groups, hydroxyl, amino or mercapto groups.

Examples are for:

Cχ-C ₂₄ alkyl groups methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. -Butyl, tert. -Butyl, pentyl, isopentyl, neopentyl, tert. -Pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl, octadecyl, octadecyl (the names above

Isooctyl, isononyl, isodecyl and isotridecyl are trivial names and come from the alcohols obtained after oxo synthesis - cf. also Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436);

C ₂ -C ₂₄ alkenyl groups vinyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl;

C ₂ -C ₂₄ alkynyl groups ethynyl, 1- or 2-propynyl, 1-, 2- and 3-butynyl;

C ₂ -C ₈ ~ alkoxyalkyl groups 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3- Propoxyproρyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3, 6-dioxaheptyl, 3, 6-dioxaoctyl, 4, 8-dioxanonyl, 3, 7-dioxaoctyl, 3, 7-dioxanonyl, 4, 7-dioxaoctyl, 4, 7-dioxanonyl, 2- and 4-butoxybutyl, 4, 8-dioxadecyl, 3, 6, 9-trioxadecyl and 3,6,9 Trioxaundecyl;

C ₃ -C ₂ cycloalkyl groups, which are optionally substituted, cycloheptyl, cyclooctyl, cyclohexyl, cyclopentyl, methylcyclohexyl and its corresponding isomers;

five- or six-membered heterocyclic radicals which contain at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur and are optionally substituted, piperidin-1-yl, piperidin-2-yl, piperidin-3-yl and piperidin-4- yl, morpholin-4-yl, morpholin-3-yl and morpholine-2-yl, piperazin-1-yl and piperazin-2-yl, 2, 2, 6, 6-tetramethyl-piperidin-1-yl, 2,2,6,6-tetramethylpiperidin-3-yl and 2,2,6,6-Te- tramethylpiperidin-4-yl, 1,2,2,6, 6-pentamethylpiperidin-3-yl and 1,2,2,6, 6-pentamethylpiperidin-4-yl, dioxan-2-yl, tetrahydrofuran-3- yl and tetrahydrofuran-2-yl, pyrrolidin-1-yl, pyrrolidin-2-yl and pyrrolidin-3-yl;

C ₆ ^_ C ₂ o ^_ aryl groups, which are optionally substituted, phenyl, naphthyl, anthracenyl, 2-hydroxyphenyl, benzyl, 2-phenylethyl and 4-tert. -Butylbenzyl;

Component (b) of the stabilizer mixtures according to the invention preferably contains at least one organic phosphite, organic phosphine or organic phosphonite selected from the group of the compounds of the general formulas (VI) to (XV):

R

R _'17

\

P- -R'- (XIII)

/

R ' _l7

in what mean

n '2, 3 or 4;

p '1 or 2;

g '2 or 3; r 'is an integer from 4 to 12;

y '1, 2 or 3;

z 'is an integer from 1 to 6;

A 'for n' is 2 a C -C ₁₈ alkylene group, - a C ₂ -Cι alkylene group which contains an oxygen or sulfur atom or an NR ' ₄ group; a group of the general formula:

a group of the general formula:

or

a phenylene group;

for n 'is 3 a group -C _r Η ₂ r'-ι- / wherein r' has the meaning given above; and

for n 'is 4 a group of the general formula

A "for q 'is 2 or 3 has the same meaning as A' for n 'is 2 or 3; B 'a single chemical bond; a group -CH ₂ -, -CHR ' ₄ - or -CR'ιR' ₄ -; a sulfur atom; a Cs-Cv cycloalkylidene; a cyclohexylidene substituted with one to four C ₄ alkyl groups in the 3-, 4- and / or 5-position;

B "optionally by H, N (-CC ₂₄ alkyl), P (C _α -C ₂₄ alkyl),

Oxygen or sulfur interrupted -C-C ₃ o-alkylene; optionally interrupted by NH, N (-CC ₂₄ alkyl), P (-C ₂₄ alkyl), oxygen or sulfur mono- or polyunsaturated C ₁ -C ₃ o-alkylidene; optionally by NH,

N (Cι-C ₂₄ alkyl), P (Cι-C ₂₄ alkyl), oxygen or sulfur interrupted C ₅ -C ₇ -cycloalkylidene; C ₆ -C ₂₄ aryl or C ₅ ~ C ₂₄ heteroarylene optionally substituted with C ₁ -C ₂₄ alkyl, C ₃ -Ci ₂ cycloalkyl or -C-Ci ₈ ~ Al oxy;

D '^•' for p 'is 1 a methyl group; and

for p 'is 2 a group -CH ₂ OCH ₂ -;

E 'for y' is 1 a -CC ₄ alkyl; a group -OR'i; or halogen;

for y 'is 2 a group -0-A "-0-, where A" has the same meaning as A' for n 'is 2; and

for y 'is 3 a group R' ₄ C (CH ₂ 0-) ₃ , N (CH ₂ CH ₂ 0-) ₃ ;

Q 'is a z' -valent radical of an alcohol or phenol which is in each case bound to the phosphorus atom via an oxygen atom;

R'i, ' ₂ and R' _{3 are} independently hydrogen; a group

-COOR ' ₄ - or -C0NR' ₄ R '₄; Cι ~ C ₂₄ alkyl, which contains an oxygen or sulfur atom or a group -NR ' ₄ -; C ₇ -C ₉ phenylalkyl; C ₃ -Ci ₂ cycloalkyl; phenyl or naphthyl optionally substituted with halogen or one to three C 1 -C ₂₄ -alkyl, C ₁ -C ₂ -alkoxy or C ₇ -Cg-phenylalkyl groups; or a group of the general formula:

wherein m 'represents an integer from 3 to 6;

R 'is hydrogen .; -CC ₂₄ alkyl; C ₃ -Ci ₂ cycloalkyl; C ₇ -Cg phenylalkyl;

R's and R's are independently hydrogen; -C ₆ alkyl; C ₅ -C6-

cycloalkyl;

R ' ₇ and R' ₈

for q 'is 2 independently of one another C 1 -C ₄ -alkyl or together a pentamethylene group;

for q 'is 3 each a methyl group;

R ' _{1 is} hydrogen; Ci-Cg alkyl; cyclohexyl;

R _'15 . Hydrogen; a methyl group;

X 'and Y' are a single chemical bond; an oxygen atom;

Z 'is a single chemical bond; a methylene group; a group -C (R'i6) 2 ~; ^e i ⁿ sulfur atom;

R _'16 is C ₁ -C ₆ alkyl;

R _'17 and R'i _{8 are} independently hydrogen; optionally interrupted by NH, N (-CC ₂₄ alkyl), oxygen or sulfur -CC ₂₄ alkyl; C ₇ -C ₉ phenylalkyl; mono- or polyunsaturated C ₂ -C ₄ alkenyl; C -C ₂₄ ~ alkynyl; C ₂ -C ₈ alkoxyalkyl; optionally substituted C ₃ -C ₂ cycloalkyl; optionally substituted C ₅ -C ₂₄ heteroaryl; optionally substituted C ₆ -C ₂ o-aryl; -C-C ₃ o-arylalkyl; C -C ₂₄ alkoxy.

Component (b) of the stabilizer mixtures according to the invention particularly preferably contains at least one organic phosphite, organic phosphine or organic phosphonite selected from the group of the compounds of the general formulas (VI), (VII), (X) and (XI), in which

n 'is 2;

y 'is 1, 2 or 3;

A 'is a C ₂ -C 8 alkylene group; a p-phenylene or p-biphenylene group; E 'for y' is 1 a -CC ₁₈ alkyl; a group -OR'x; or fluorine;

for y 'is 2 a p-biphenylene group; and

for y 'is 3 a group N (CH ₂ CH ₂ 0-) ₃ ;

R'i, R 'and R' independently of one another are C -C ₈ alkyl; C ₇ -Cg phenylalkyl; cyclohexyl; phenyl optionally substituted with one to three Ci-Cis-alkyl groups;

R ' _{4 is} hydrogen; Ci-Cg alkyl;

R'i _{5 is} hydrogen; a methyl group;

X '^•' single chemical bond;

Y 'is an oxygen atom;

Z 'is a single chemical bond; a group -C (R '6) ₂ ^_ ;

R _'16 is C 1 -C ₄ alkyl.

Further particularly preferred organic phosphites or organic phosphonites of component (b) of the stabilizer mixtures according to the invention are selected from the group of compounds of the general formulas (VI), (VII), (X) and (XI), in which

n 'is 2;

y 'is 1 or 3;

A 'is a p-biphenylene group

E 'for y' is 1 is a Ci-Cis-alkyl; Fluorine;

for y 'is 3 a group N (CH ₂ CH ₂ 0-) ₃ ;

R'i, R ' ₂ and R' ₃ independently of one another are C ₂ -C 1 -alkyl; phenyl substituted with two to three C ₂ -C ₂ alkyl groups;

R'i _{4 is} methyl or tert. butyl group;

R'i _{5 is} hydrogen;

X 'single chemical bond; Y 'is an oxygen atom;

Z 'is a single chemical bond; a methylene group; a group -CH (CH ₃ ) -;

Further particularly preferred organic phosphites of component (b) of the stabilizer mixtures according to the invention are those of the general formula (XVI)

in what mean

R "and R" _{2 are} independently hydrogen; Ci-Cs-alkyl; Cy-c1ohexyl; Phenyl;

R " ₃ and R" _{4 are} independently hydrogen; -CC ₄ alkyl;

Examples of phosphites and phosphonites of component (b) of the stabilizer mixtures according to the invention are: triphenylphosph.it; diphenyl; phenyldialkylphosphites; Tris (nonylphenyl) phosphite (commercially available under the brand name Alkano TNPP; Great Lakes Chemical Corp.); trilaurylphosphite; trioctadecyl; distearyl; Tris (2, -di-tert-butylphenyl) phosphite (commercially available under the brand name Alkanox 240; Great Lakes Chemical Corp.); diisodecyl pentaerythritol diphosphite; Bis (2, -di-tert-butylphenyldpentaerythritol diphosphite (commercially available under the brand name Alkanox P24; Great Lakes Chemical Corp.); bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite; bis ( isodecyl) pentaerythritol diphosphite; bis (2, -di-tert.-butyl-6-methylphenyl) pentaerythritol diphosphite; bis [2,4, 6-tris (t-butyl) phenyl] pentaerythritol diphosphite; tris stearyl sorbitol diphosphite; Tetrakis (2, -di-tert.-butylphenyl) -4, 4 '-diphenylenediphosphonite (commercially available under the brand name Alkano 24-44; Great Lakes Chemical Corp.); 6-isooctyloxy-2, 4, 8, 10 -tetra-tert-butyl-12H-dibenzo- [d, g] -1,3, 2-dioxaphosphocin _/ 6-fluoro- 2,4,8, 10-tetra-tert-butyl-12-methyldibenzo [d , g] -1, 3, 2-dioxaphosphine; bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite; bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (commercial available under the brand name Irgafos ^ 38; Ciba Specialty Chemicals); Bis (2,4-dicumylphenyl) pentaerythritol diphosphite.

The following are particularly worth mentioning: tris (2,4-di-tert-butylphenyl) phosphite; Tris (nonylphenyl) phosphite; 6-fluoro-2, 4, 8, 10-tetra-tert. -butyl-12-methyldibenzo [d, g] -1, 3, 2-dioxaphosphocin; 6-iso-octyloxy-2, 4,8, 10-tetra-tert. -butyl-12H-dibenzo- [d, g] -1, 3, 2-dioxa-phosphocin; Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite; Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite; Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite; Bis (2,4-dicumylphenyl) pentaerythritol diphosphite; Tetrakis (2,4-di-tert-butylphenyl) -4,4'-diphenylene diphosphonite; the triphosphite of the formula (XVII)

and the diphosphite of formula (XVIII)

37 cj. β ₇ (xvill).

In particular, the component (b) here is the organic phosphites and phosphonites: tris (nonylphenyl) phosphite; Tris (2,4-di-tert-butylphenyl) phosphite; Bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite; Tetrakis (2,4-di-tert-butylphenyl) -4,4'-diphenylene diphosphonite; and highlight bis (2, 4-dicumylphenyl) pentaerythritol diphosphite.

The organic phosphites and phosphonites of component (b) listed above are known compounds, many of which are commercially available. Sterically hindered phenols as optional component (c) of the stabilizer mixtures according to the invention preferably obey the general formula (XIX)

in what mean

R ₁ '-C ₄ alkyl;

n "is a number 1, 2, 3 or 4;

X "is a methylene group; or a group of the general formulas (XX) or (XXI)

0 -CH ₂ -CH ₂ -CY "- (XX);

CH _j _C-O-CH ₂ -CH ₂ (XXI);

wherein Y "represents an oxygen atom; or a group -NH-;

where X "corresponds

for n "is 1 of a group of the general formula (XX) in which Y" is bonded to R ₂ 'and R ₂ ' is C -C ₂₅ alkyl;

for n "is equal to 2 of a group of the general formula (XX) in which Y" is bonded to 'and R ₂ ' is a C ₂ -C ₂ alkylene group; a C ₄ ~ -C ₂ alkylene group, which contains one or more oxygen or sulfur atoms, means; where in the case that Y "represents a group -NH-, R ₂ 'represents a single chemical bond; for n "is 3 a methylene group; a group of the general formula (XXI) in which the ethylene group is bonded to R ₂ 'and R ₂ ' is a group of the formula (XXII)

corresponds;

for n "is 4 of a group of the general formula (XX), in ^• 'which Y" is bonded to R ₂ and R ₂ ' corresponds to a C ₄ -C ~ alkane tray group.

Examples of linear and branched C 1 -C ₂₅ alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec. Butyl, tert. -Butyl, 2-ethylbutyl, pentyl, 1-methylpentyl, isopentyl, neopentyl, tert. -Pentyl, hexyl, 1, 3-dimethylbutyl, 2-methylpentyl, heptyl, isoheptyl, 1-methylhexyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, 1,1,3, 3-tetramethylbutyl, 1-methylheptyl , 3-methylheptyl, nonyl, isononyl, 1,1,3,3-tetramethylpentyl, decyl, 1, 1, 3-trimethylhexyl, isodecyl, undecyl, dodecyl, 1-methyl-undecyl, 1, 1, 3, 3 , 5, 5-hexamethylhexyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and doeicosyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are derived from trivial names and are derived from the same names as trivial deroxes alcohols obtained - cf. üllmann's Encyklopadie der Technische Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436);

Ri 'preferably corresponds to a methyl or tert. Butyl group.

For n "equal to 1, R ₂ 'preferably corresponds to a C 1 -C ₂ -alkyl, in particular a C ₄ -Cs-alkyl group. Particularly important for R ₂ ' are Cg-Ci ₈ -alkyl, and in particular Ci ₄ -Ci ₈ ~ alkyl groups, such as octadecyl to emphasize.

For n "equal to 2, R ₂ 'usually corresponds to a C ₂ -C o -alkylene, preferably a C ₂ -Cs alkylene group. In particular, R' corresponds to a C ₄ -C ₈ alkylene, particularly preferably a C ₄ - C6 alkylene group, such as, for example, hexamethylene optionally also contain one or more oxygen or sulfur atoms.

Examples of linear or branched C ₂ -C ₂ alkylene groups are ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene and dodecamethylene.

Examples of C ₄ -Ci ₂ alkylene groups which contain one or more oxygen or sulfur atoms are -CH ₂ -0-CH ₂ CH ₂ -0-CH ₂ -, -CH ₂ - (0-CH ₂ CH ₂ ) ₂ -0-CH ₂ -,

-CH ₂ - (0-CH ₂ CH ₂ ) ₃ -0-CH ₂ -, -CH ₂ - (0-CH ₂ CH ₂ ) -0-CH ₂ - and especially -CHCH ₂ -0-CH ₂ CH ₂ -0-CH ₂ CH ₂ - and -CH ₂ CH ₂ -S-CH ₂ CH ₂ -.

Examples of C ₄ -Cχo-alkanetetrayl groups for R ₂ 'when n "is 4 are

CH ₂ - ^CH a - - ^{C --— CH} 2 - (pentaerythritol)

-CH ₂ -CH-CH-CH ₃ .

-CH ₂ -CH ₂ -CH — CH- .CH, -

CH ₂ _CH ₂ _CH_CH — CH ₂ -CH ₂ -,

CH-, -CHj -CH-CE. —CH — CH-, —CH _j -.

CH ₂ -CH _a -C IH — CH ₃ -CH ₂ -C IH CH ₂ —CH ₂ -

the pentaerythritol residue being preferred. In accordance with the abovementioned preferences, preferred sterically hindered phenols as optional component (c) in the stabilizer mixtures according to the invention are those in which, for n ″ equal to 1 in the general formula (XIX), the radical R ₂ ′ denotes a C ₁ -C ₂ -alkyl group ,

In accordance with the abovementioned preferences, preferred sterically hindered phenols as optional component (c) in the stabilizer mixtures according to the invention are also those in which, for n ″ equal to 2 in the general formula (XIX), the radical R ₂ ′ is a C ₂ -C ₆ alkylene group , a C -C ₈ alkylene group which contains one or more oxygen or sulfur atoms, or, in the case where Y "represents a group -NH-, a chemical single bond.

Furthermore, preferred sterically hindered phenols as optional component (c) in the stabilizer mixtures according to the invention are also those in which, for n ″ equal to 4 in the general formula (XIX), the radical R ₂ ′ is one of the C ₄ -C ₆ -alkantetrayl group shown by way of example means.

Preferred sterically hindered phenols as optional component (c) in the stabilizer mixtures according to the invention are also those in which in the general formula (XIX) Ri 'a methyl or tert. -Butyl group, n "has a value of 1, 2 or 4, X" corresponds to a group (XX) and Y "corresponds to an oxygen atom or a group -NH-, where for

n "is 1, R ₂ 'is a C ^ -Cis alkyl group,

n "is equal to 2, R ₂ 'is a C ₄ -C ₆ alkylene or one, one or more oxygen or sulfur atoms containing C ₄ -C ₆ alkylene group

n "is 4, R ₂ 'is a C ₄ -C ₆ alkanetrayl group.

With regard to the stabilizer mixtures according to the invention, sterically hindered phenols which correspond to the general formula (XIX) and are assigned to the group listed below are of interest as optional component (c): N, N'-hexamethylene bis [3- (3, 5- di-tert-butyl-4-hydroxyphenyl) propionamide] (commercially available under the trademark Lowinox® HD-98; Great Lakes Chemical Corp.); Octadecyl-3- (3 ', 5'-di-tert-butyl-4' -hydroxyphenyl) propionate (commercially available under the brand name Anox ™ PP18; Great Lakes Chemical Corp.); Tetrakismethylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) methane (commercially available under the brand name Anox ™ 20; Great Lakes Chemical Corp.); Triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methyl- phenyl) propionate] (commercially available under the trademark Lowinox® GP-45; Great Lakes Chemical Corp.); 2,2 '-Thiodiethylene bis [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (commercially available under the brand name Anox ™ 70; Great Lakes Chemical Corp.); 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate (commercially available under the brand name Anox ™ IC-14; Great Lakes Chemical Corp.); the compound of formula

(commercially available under the brand name Irganox® 259; Ciba Specialty Chemicals); the compound of formula

(Commercially available under the brand name Irganox® 3125; Ciba Specialty Chemicals).

Further preferred sterically hindered phenols as optional component (c) of the stabilizer mixtures according to the invention are those which contain a sterically hindered phenol group of the general formulas (I ') or (I'a)

included, the variables R'i and R ' ₂ independently of one another having the meaning given above.

In particular, here are compounds of the general formulas (II ') and (Il'a)

of interest. Compounds of the formulas (II ') and (Il'a) and compounds which contain groups of the formulas (I') and (I'a) are described in the documents EP 162 523 A2 and EP 182 415 A2 which is expressly referred to here. Because of the hydrolyzable silyl residues, the compounds shown above can provide complex and highly viscous hydrolysis and / or condensation products. An example of the abovementioned compounds containing silyl groups is shown below in the general formula (II "):

The "compound" consists of a mixture consisting of linear oligomers, in which Ri is hydroxyl and R ₂ is hydrogen, and cyclic oligomers, in which Ri and R ₂ each represent a single chemical bond, with an average molecular weight of 3,900 g / mol.

As already mentioned above, the sterically hindered phenols are known as optional component (c) and in some cases are also commercially available. In addition, other of these connections e.g. also according to the documents US 3,330,859,

US 3,960,928, EP 162 523 A2 and EP 182 415 A2.

Sterically hindered amines may also be present in the stabilizer compositions according to the invention as a further optional component (d). These compounds contain at least one grouping of the general formulas (XXIII) or (XXIV)

(XXIII)

contain what mean

G hydrogen; a methyl group;

Gi and G _{2 are} independently hydrogen; a methyl group; or together an oxygen atom.

The stabilizer mixtures according to the invention preferably contain, as optional component (d), sterically hindered amines which are selected from the groups (a ') to (h') of compounds listed below and which have at least one of the abovementioned groups of the general formulas (XXIII ) or (XXIV).

Group (a '): Compounds of the general formula (XXV):

in what mean

n is an integer from 1 to 4;

G and Gi are independently hydrogen or a methyl group;

Gn hydrogen, oxygen (N-Gn then forms a nitroxyl group), hydroxy, a group NO (nitroso group), a group -CH ₂ CN, Ci-Cie-alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ -alkynyl, C ₇ -Cι ₂ _ arylalkyl, Ci-Cis-alkoxy, C ₅ -C ₈ cycloalkoxy, C ₇ -Cg-phenylalkoxy, Ci-Cs-alkanoyl, C ₃ -C ₅ -alkenoyl, Ci -Cis alkanoyloxy, berizyloxy, glycidyl; a group -CH ₂ CH (0H) -Z, in which Z was- means hydrogen, methyl or phenyl; preferably hydrogen, -CC ₄ ~ alkyl, allyl, benzyl, acetyl or acryloyl;

for n is 1 hydrogen, Ci-Cis-alkyl, which optionally contains one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, unsaturated or aromatic cycloaliphatic or arylaliphatic 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, a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, an α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms, an aromatic carboxylic acid

7 to 15 carbon atoms, these carboxylic acids being optionally substituted in the aliphatic, cycloaliphatic or aromatic part with one to 3 groups -COOZ ₁₂ and Z _i2 for hydrogen, C ₁ -C ₂ -alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, phenyl or benzyl;

for n is 2, C ₂ -C ₂ alkylene, C ₄ -C ₂ alkenylene, a xylylene group, a divalent radical of an aliphatic, cycloaliphatic, arylaliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid, or a divalent silyl radical , preferably a residue of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, a cycloaliphatic or aromatic dicarboxylic acid

8 to 14 carbon atoms, an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8 to 14 carbon atoms, these carboxylic acids optionally being substituted in the aliphatic, cycloaliphatic or aromatic part with one or 2 groups -COOZι ₂ and Z _{12 has} the meaning given above;

for n is 3, a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which carboxylic acid is optionally substituted in the aliphatic, cycloaliphatic or aromatic part with a group -COOZ ₁₂ and Zι _{2 has} the meaning given above, an aromatic tricarboxylic acid, one phosphoric acid, or a trivalent silyl radical; and

for n equal to 4 a tetravalent residue of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid. Examples of C ₁ -C ₂ -alkyl groups are: methyl, ethyl, n-propyl, n-butyl, sec. -Butyl, tert. -Butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.

Examples of -CC ₈ -alkyl groups for Gn and Gχ are in

Supplement to the groups already mentioned: n-tridecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

Examples of C ₃ -Cg alkenyl groups for Gn are: 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl and 4-tert. -Butyl-2-butenyl.

Propargyl is preferred as the C ₃ -C ₈ alkynyl group for Gn.

As C 1 -C ₂ arylalkyl group for Gn, phenylethyl, in particular benzyl, is particularly suitable.

Examples of Ci-C _ß alkanoyl groups for Gn are: formyl, propionyl, butyryl, octanoyl, especially acetyl and, in the case of a C ₃ -C ₅ alkanoyl group, preferably acryloyl.

Examples of monovalent carboxylic acid residues for Gι _{2 are} derived from acetic acid, caproic acid (hexanoic acid), stearic acid (octadecanoic acid), acrylic acid, methacrylic acid, benzoic acid and ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ,

Examples of monovalent silyl radicals for G12 are: a radical of the general formula - (C _j H _{2: j} ) -Si (Z ') ₂ Z ", where j is an integer from 2 to 5 and Z' and Z" independently of one another C 1 -C ₄ alkyl or C 1 -C ₄ alkoxyl group.

Examples of divalent carboxylic acid residues for G _{12 are} derived from malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid (suberic acid, octanedioic acid), sebacic acid, maleic acid, itaconic acid (methylene succinic acid), phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, 5-butyl acid, di-tert-butyl-4-hydroxybenzyl) alonic acid and bicycloheptenedicarboxylic acid.

Examples of trivalent carboxylic acid residues for G _{2 are} derived from trimellitic acid, citric acid and nitrilotriacetic acid.

Examples of tetravalent tetracarboxylic acid residues for G _{2 are} derived from butane-1, 2, 3, -tetracarboxylic acid and pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid). Examples of divalent dicarbamic acid residues for G ₂ derive from hexamethylene dicarbamic acid and 2,4-toluenedicarbamic acid.

5 Preferred compounds of the general formula (XXV) are those in which G is hydrogen, Gn is hydrogen or methyl, G _{2 is} a diacyl radical of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and n is 2.

10 examples of polyalkylpiperidms of the general formula (XXV) are in particular:

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

2) l-allyl-4-hydroxy-2, 2,6, 6-tetramethylpiperidine;

15 3) 1-Benzyl-4-hydroxy-2, 2,6, 6-tetramethylpiperidine;

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

5) 4-stearyloxy-2, 2,6, 6-tetramethylpiperidine;

6) l-ethyl-4-salicyloyloxy-2, 2,6, 6-tetramethylpiperidine;

20 7) 4-methacryloyloxy-l, 2,2,6, 6-pentamethylpiperidine, -

8) 1,2,2,6,6-pentamethylpiperidin-4-yl-ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate;

9) di (l-benzyl-2, 2,6, 6-tetramethylpiperidin-4-yl) maleate; 10 di (2, 2, 6, 6-tetramethylpiperidin-4-yl) succinate;

25 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 (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) sebacate; 15 di (1, 2, 3, 6-tetramethyl-2, 6-diethylpiperidin-4-yl) sebacate;

30 16 di (l-allyl-2, 2,6, 6-tetramethylpiperidin-4-yl) phthalate; 17 l-hydroxy-4-ß-cyanoethyloxy-2, 2,6, 6-tetramethylpiperidine; 18 l-acetyl-2, 2,6, 6-tetramethylpiperidin-4-yl acetate; 19 tris (2,2,6, 6-tetramethylpiperidin-4-yl) trimellitate; 20 l-acryloyl-4-benzyloxy-2, 2,6, 6-tetramethylpiperidine; ,

35 21 di (2, 2, 6, 6-tetramethylpiperidin-4-yl) diethylmalonate; 22 di (1, 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; 40 25 di (l-cyclohexyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate;

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

27 toluene-2 ', 4' bis (4-carbamoyloxy-1-n-propyl-2, 2,6, 6-tetra-methylpiperidine);

45 28 dimethyl-bis (2,2,6, 6-tetramethylpiperidine-4-oxy) silane;

29 phenyl-tris (2,2,6, 6-tetramethylpiperidine-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) bis (1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) phenylphosphonate; 33) 4-hydroxy-l, 2,2,6, 6-pentamethylpiperidine;

34) 4-hydroxy-N-hydroxyethyl-2, 2,6, 6-tetramethylpiperidine;

35) 4-Hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine; 36) 1-Glycidyl-4-hydroxy-2, 2,6, 6-tetramethylpiperidine.

Group (b '): Compounds of the general formula (XXVI):

in what mean

n 1 or 2;

G, Gi and Gn have the same meaning as under group (a ');

G ₁₃ hydrogen, C ₁ -C ₂ -alkyl, C ₂ -C ₅ -hydroxyalkyl, C ₅ -C -cycloalkyl-, C ₇ -C ₈ -arylalkyl, formyl, C ₂ -Ci ₈ -alkonoyl, C ₃ - Cs-alkenoyl, benzoyl or a group of the general formula

G ₁₄ for n is 1, hydrogen, C ₁ -C ₅ -alkyl, C ₃ -C ₈ -alkenyl,

C ₅ -C Cycloalkyl, with hydroxy, cyano, alkoxycarbonyl or carbamide substituted -CC ₄ ~ alkyl, glycidyl, a group of the formula -CH ₂ -CH (0H) -Z or the formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl, in the event that G _{13 is} not alkanoyl, alkenoyl or benzoyl, or G ₁₃ and G ₁₄ together form a divalent radical of an aliphatic, cycloaliphatic or aromatic 1,3-dicarboxylic acid; for n is 2, C ₂ -Ci ₂ -alkylene, C ₆ -Cι ₂ -arylene, a xylylene group, a group of the formula -CH ₂ -CH (OH) -CH- or a group of the formula -CH ₂ - CH (OH) -CH ₂ -0-D-0, in which DC ₂ -Cι ₀ -alkylene, C ₆ -Cιo arylene or C ₆ -Cι ₂ cycloalkylene means; a 1-oxo (C ₂ -C ₂ ) alkylene group, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic or dicarbamic acid, or -CO-; or G ₃ and G ₁₄ on the 4 nitrogen atom of each of the two piperidinyl residues together form a residue of the formula

Possible C 1 -C ₂ alkyl or C ₁ -C 4 alkyl groups have already been described as examples under group (a ').

Cyclohexyl is preferably used as C5-C-cycloalkyl.

Suitable arylalkyl for G13 is phenylethyl, preferably benzyl.

Examples of suitable C ₂ -C 5 hydroxyalkyl for G ₁ 3 are 2-hydroxyethyl and 2-hydroxypropyl.

Examples of C ₂ -C 8 alkanoyl for G ₁₃ are: propionyl, butyryl,

Octanoyl, dodecanoyl, hexadecanoyl and octadecanoyl. Particular mention should be made of acetyl and, in the event that G ₃ . _{3 is} C ₃ -C ₅ alkenoyl, preferably acryloyl.

Examples of C -Cs alkenyl for G ₁₄ are: Allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl and 2-0ctenyl.

Examples of C 1 -C ₄ -alkyl which is substituted by hydroxy, cyano, alkoxycarbonyl or carbamide are: 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl and 2- (Dirnethylaminocarbonyl) ethyl. Examples of C ₂ -C ₂ alkylene are: ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene.

Examples of C ₆ -C ₅ arylene are: o-, m- or p-phenylene, 1, 4-naphthylene and 4,4'-diphenylene.

As C ₆ -C ₂ cycloalkylene, cyclohexylene is particularly suitable.

Preferred compounds of the general formula (XXVI) are those in which n is 1 or 2 and G is hydrogen, ^' Gn' hydrogen or methyl, Gι hydrogen, formyl -CC-C ₂ alkyl or a group of the formula

and

G ₁₄ for n is 1, hydrogen or -CC ₂ alkyl and

for n is 2, C -C ₈ alkylene or a 1-oxo (C ₂ -Cs) alkylene group

means.

Examples of polyalkylpiperidines of the general formula (XXVI) are in particular:

1) N, N 'bis (2,2,6, 6-tetramethylpiperidin-4-yl) hexamethylene-1, 6-diamine;

2) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) examethylene-1,6-diacetamide;

3) bis (2,2,6, 6-tetramethylpiperidin-4-yl) amine; 4) 4-benzoylamino-2, 2,6, 6-tetramethylpiperidine;

5) N, N'-bis (2,2,6, 6-tetramethylpiperidin-4-yl) -N, N '-di-butyladipamide;

6) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-di-cyclohexyl-2-hydroxypropylene-1,3-diamine ₇ 7) N, N '-Bis (2,2,6, 6-tetramethylpiperidin-4-yl) -p-xylylenediamine; 8) N, N'-bis (2,2,6, 6-tetramethylpiperidin-4-yl) succinamide; 9) bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) -N- (2, 2, 6, 6-tetra-methylpiperidin-4-yl) -ß-aminodipropionate;

10) a compound of the formula:

11) 4- [bis (2-hydroxyethyl) amino] -1,2,2,6,6-pentamethylpiperidine; 25 12) 4- (3-Methyl-4-hydroxy-5-tert-butylbenzamido) -2,2,6,6-tetra-methylpiperidine;

13) 4-methacrylamido-l, 2,2,6, 6-pentamethylpiperidine;

14) N, N'-bisformyl-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine (commercially available under the trademark)

30 men Uvinul ^® 4050 H; BASF Aktiengesellschaft);

15) N, N'-bisformyl-bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) hexamethylene-1,6-diamine;

16) a compound of the formula

(commercially available under the brand name Uvinul 4049 H; BASF Aktiengesellschaft);

45 17) a compound of the formula

Group (c '): compounds of the general formula (XXVII)

(XXVII)

in what mean

n 1 or 2;

G, Gi and Gn have the same meaning as under group (a ');

G ₁₅ for n is 1, C ₂ -Cs-alkylene, C ₂ -Cs-hydroxyalkylene or C ₄ -C ₂ -acyloxyalkylene and

for n is 2, a group (CH) ₂ C (CH ₂ -) ₂ .

Examples of C ₂ -Cs alkylene or C ₂ -Cs hydroxyalkylene for G ₁₅ are: ethylene, 1-methylethylene, propylene, 2-ethylpropylene and 2-ethyl-2-hydroxymethylpropylene.

An example of C ₄ -C ₂₂ acyloxyalkylene for G ₁₅ is 2-ethyl-2-acetoxymethylpropylene.

Examples of polyalkylpiperidines of the general formula (XXVII) are in particular:

1) 9-aza-8, 8,10, 10-tetramethyl-l, 5-dioxaspiro [5.5] undecane;

2) 9-aza-8, 8,10, 10-tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] undecan;

3) 8-aza-2, 7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane; 4) 9-aza-3-hydroxymethyl-3-ethyl-8, 8,9,10, 10-pentamethyl-l, 5-dioxaspiro [5.5] undecane; 5) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8, 8,10, 10-tetramethyl-

1, 5-dioxaspiro [5.5] undecane; 6) 2,2, 6, 6-tetramethylpiperidine-4-spiro-2 '- (1', 3 '-dioxane) -5' - spiro-5 "- (l", 3 "-dioxane) -2" - spiro-4 "'- (2"', 2 "', 6"', 6 "'- tetramethylpiperidine).

Group (d '): Compounds of the general formulas (XXVIIIA), (XXVIIIB) and preferably (XXVIIIC):

(XXVIIIA)

VIIIB)

(XXVIIIC)

in what mean

n 1 or 2;

G, Gi and Gn have the same meaning as under group (a ');

Gi ₆ hydrogen, -C ~ -C-alkyl, allyl, benzyl, glycidyl or C ₂ -C6 alkoxyalkyl;

G ₁₇ for n is 1, hydrogen, C ₁ -C ₂ alkyl, C ₃ -C ₅ alkenyl,

C ₇ -Cg-arylalkyl, C ₅ -C ₇ -cycloalkyl, CC ₄ -hydroxyalkyl, CC ₆ -alkoxyalkyl, Cg-Cio-aryl, glycidyl or a group of the formula - (CH ₂ ) p-COO-Q or - (CH ₂ ) _p -0-CO-Q, where p is 1 or 2 and Q is C 1 -C ₄ -alkyl or phenyl, and

for n is 2, C ₂ -C ₂ alkylene, C ₄ -C ₁ alkenylene, C ₆ -C ₂ arylene, a group of the formula:

-CH ₂ -CH (OH) -CH ₂ -0-D-0-CH ₂ -CH (OH) -CH ₂ -,

wherein DC ₂ -Cιo alkylene, C ₆ -Ci ₅ arylene, C ₆ -Cι ₂ cycloalkylene means, or a group of the formula:

-CH ₂ CH (OZ ') CH ₂ -0CH ₂ -CH (OZ') CH ₂ -0CH ₂ -CH (OZ ') CH ₂ -

wherein Z 'is hydrogen, Ci-Cie-alkyl, allyl, benzyl, C -C ₂ -Al- kanoyl or benzoyl;

i and Ti are, independently of one another, hydrogen, C 1 -C ₄ -alkyl optionally substituted with halogen or C 1 -C ₄ alkyl, C 1 -C ₄ -aryl optionally substituted with halogen or C 1 -C ₄ alkyl, optionally with halogen or C 1 -C _{4 4-} alkyl substituted C -Cg arylalkyl; or i and T ₂ together with the carbon atom to which they are attached form a C ₅ -Ci ₄ cycloalkane ring.

Examples of C 1 -C ₂ alkyl are: methyl, ethyl, n-propyl, n-butyl, sec. -Butyl, tert. -Butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl.

Examples of Ci-Ciβ-alkyl, in addition to the previously-exemplified Cι-Cι ₂ alkyl radicals: n-tridecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

Examples of C ₂ -C ₆ alkoxyalkyl are: methoxymethyl, ethoxymethyl, propoxymethyl, tert. -Butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert. -Butoxyethyl, isopropoxyethyl and propoxypropyl.

Examples of C ₃ -Cs alkenyl for G ₁₇ are: 1-propenyl, allyl, methallyl, 2-butenyl and 2-pentenyl.

Examples of C ₇ -Cg arylalkyl for G _i , Ti and T ₂ are: phenylethyl, preferably benzyl.

Examples for the case in which i and T ₂ form cycloalkane rings with the carbon atom to which they are attached: cyclopentane, cyclohexane, cyclooctane and cyclododecane. Examples of C ₂ -C ₄ hydroxyalkyl for Gι are: 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl and 4-hydroxybutyl.

Examples of Coe-Cio-aryl G _17, T and T ₂ are optionally substituted with halo or _Cι-C4 alkyl substituted phenyl, and optionally substituted with halo or Cι-C ₄ alkyl substituted α- or ß-naphthol thyl.

Examples of C ₂ -C alkylene for G ₁₇ are: ethylene, propylene, 2, 2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene.

Examples of C ₄ -C ₂ alkenylene for G ₁₇ are: 2-butenylene, 2-pentenylene and 3-hexenylene.

Examples of C ₆ -C ₂ -arylene for G ₁₇ are: o-, m- and p-phenylene, 1, 4-naphthylene and 4, 4'-diphenylene.

Examples of C ₂ -C ₂ alkanoyl for Z are: propionyl, butyryl, octanoyl and dodecanoyl, preferably acetyl.

Examples of C ₂ -C ₀ alkylene, C ₆ -C ₅ arylene and C ₆ -C ₂ cycloalkylene for D are described under group (b ').

Examples of polyalkylpiperidines of the general formulas (XXVIIIA), (XXVIIIB) and (XXVIIIC) are in particular:

1) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylεpiro [4.5] decan-2,4-dione; 2) 3-n-octyl-l, 3,8-triaza-7,7,9,9-tetramethylspiro [4.5] decan-2, 4-dione;

3) 3-Allyl-1,3,8-triaza-l, 7,7,9,9-pentamethylspiro [4.5] decan-2,4-dione;

4) 3-glycidyl-1, 3, 8-triaza-7, 7,8,9, 9-pentamethylspiro [4.5] decan-2, 4-dione;

5) 1,3,7,7,8,9, 9-heptamethyl-l, 3, 8-triazaspiro [4.5] decan-2, 4-dione;

6) 2-isopropyl-7, 7,9, 9-tetramethyl-l-oxa-3, 8-diaza-4-oxo-spiro [4.5] decane, - 7) 2,2-dibutyl-7,7,9 , 9-tetramethyl-l-oxa-3,8-diaza-4-oxo-spiro [4.5] decane;

8) 2,2,4,4-tetramethyl-7-oxa-3, 20-diaza-21-oxodispiro [5.1.11.2] heneicosane;

9) 2-butyl-7, 7,9, 9-tetramethyl-1-oxa-4, 8-diaza-3-oxo-spiro [4.5] decane; and preferably 10) 8-acetyl-3-dodecyl-1,3, i-triaza-7, 7,9, 9-tetramethylspiro- [4.5] decane-2, 4-dione;

and compounds of the following formulas:

CH-OH

(XXVIII) -12 i

(XXVIII) -13 j

(XXVIII) -14.

Group (s'): compounds of the general formula (XXIX)

in what mean

n 1 or 2;

Gis a group of the formula:

where G and Gn have the same meaning as under group (a ');

Gi and G ₂ independently of one another are hydrogen or methyl, or together with the carbon atom to which they are attached a carbonyl group; ^■

E oxygen or a group -NG ₁₃ -;

AC ₂ -C ₆ alkylene or a group - (CH ₂ ) ₃ -0-;

x is 0 or 1;

G _{13 is} hydrogen, -CC ₂ -alkyl, C -C ₅ -hydroxyalkyl, C ₅ -C ₇ -cycloalkyl;

G _{19 has the} same meaning as G s or one of the following groups: -NG ₂ ιG ₂₂ , -OG ₂₃ , -NHCH ₂ 0G ₂ 3 or -N (CH ₂ 0G ₂₃ ) ₂ ;

G ₂₀ for n is 1, the same meaning as G sharp or gig,

for n is 2, a group -EBE-, in which B is C ₂ -Cs-alkylene optionally interrupted by one or two -N (G ₂ ι) groups; G ₂₁ C 1 -C ₂ alkyl, cyclohexyl, benzyl, C 1 -C ₄ hydroxyalkyl, a group of the following formula:

or a group of the following formula:

G ₂₂ -C 1 -C ₂ alkyl, cyclohexyl, benzyl, C ₄ -C ₄ -hydroxyalkyl;

or G ₂ ι and G ₂ in the group -NG ₂ ιG ₂ together form a C ₄ -C ₅ alkylene or C ₄ -C ₅ oxyalkylene group, or a group of the formula:

G _{23 is} hydrogen, -CC ₂ -alkyl, phenyl.

Examples of C 1 -C ₂ alkyl are: methyl, ethyl, n-propyl, n-butyl, sec. -Butyl, tert. -Butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. Examples of C 1 -C ₄ -hydroxyalkyl are: 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl and 4-hydroxybutyl.

Examples of C ₂ -C ₆ alkylene for A are: ethylene, propylene, 2,2-dimethylpropylene, tetramethylene and hexamethylene.

In the event that G ₂ ι and G ₂₂ together form C ₄ -C ₅ alkylene or C ₄ -C ₅ oxyalkylene, the following should be mentioned: tetramethylene, pentamethylene and 3-oxapentamethylene.

Examples of polyalkylpiperidines of the general formula (XXIX) are in particular:

CH _j J a

(XXIX) -1;

R-NH- (CH ₂ ) 3-N (R) - (CH ₂ ) ₂ -N (R) - (CH ₂ ) 3-NH-R (XXIX) -6,

where R means

R-NH- (CH ₂ ) ₃ -N (R) - (CH ₂ ) ₂ -N (R) - (CH ₂ ) ₃ -NH-R (XXIX) -7,

where R means

RN (CH ₃ ) - (CH ₂ ) ₃ -N (R) - (CH ₂ ) ₂ -N (R) - (CH ₂ ) ₃ -N (CH ₃ ) -R. (XXIX) -8,

where R means

(XXIX) -9;

CHJCHJOH

(XXIX) -10;

(XXIX) -11. Group (f): Oligomeric or polymeric compounds whose recurring units 2,2,6, 6-tetramethylpiperidine-containing radicals, especially polyester, polyethers, polyamides, polyamines, poly- ^'thane, polyureas, polyaminotriazines, poly (meth) acrylates and poly (meth) acrylamides, and their copolymers

Examples of such 2, 2, 6, 6-polyalkylpiperidines are given by the following formulas, where m is a number from 2 to 200:

(XXX) -1;

(XXX) -2;

(XXX) -3;

(XXX) -4; -CHtαD-CH _j

(XXX) -5;

(XXX) -6;

(XXX) -9;

(XXX) -12 _/

(XXX) -13;

(XXX) -14;

R R

I -N-. (CH _J JJ— N— (CH ₂ ) _2. m '

where R is a residue

or

and m 'and m "each represent an integer from 0 to 200, with the proviso that m' + m" = m.

Further examples of polymeric compounds of group (f) are:

the reaction products of compounds of the formula (XXXI)

with epichlorohydrin;

- 'Polyester, which by reacting butane-1, 2, 3, 4-tetracarboxylic acid with dihydric alcohols of the formula (XXXII):

(XXXII) are obtained and their carboxyl termination originating from the tetracarboxylic acid is esterified with 2,2,6,6-tetramethyl-4-hydroxypiperidine;

Compounds of the general formula (XXXIII)

(XXXIII)

wherein about a third of the radicals R are ethyl and the remainder of the radicals R are a radical of the formula

mean and m is a number from 2 to 200;

Copolymers, the repeating units on the one hand made of α-methylstyrene

and on the other hand from maleimide derivatives of the formulas

C _j . ₃ H ₂₇

and

consist; Copolymers whose repeating units on the one hand from α-Ci ₈ ~ C ₂₈ olefins or mixtures of such olefins and on the other hand from maleimide derivatives of the formula

consist. For example, the commercially available product Uvinul® 5050 H (only hydrogen on the 1-stick of the piperidine ring; BASF Aktiengesellschaft) should be mentioned.

Group (g '): compounds of the general formula (XXXIV)

(XXXIV)

in what mean

n 1 or 2;

G and Gn have the same meaning as under group (a ') and

G _{14 has the} same meaning as under group (b '), where G ₁₄ neither represents a group -CONH-Z nor a group -CH ₂ CH (OH) -CH ₂ -0-D-0.

Examples of compounds of the general formula (XXXIV) are:

(XXXIV) - 17th

Group (h '): compounds of the general formula (XXXV ⁾

in which mean:

R _l C ₁ -C ₄ alkyl, C ₅ -C ₂ cycloalkyl optionally substituted with C ₄ alkyl, phenyl optionally substituted with C ₁₀ alkyl;

R ₂ C ₃ -C ₁₀ alkylene;

R ₃ hydrogen, C _! -C ₈ alkyl, 0-, -CH ₂ CN, C ₃ -C ₆ alkenyl, optionally substituted on the phenyl radical with -C ~ C ₄ alkyl substituted C ₇ -Cg phenylalkyl, Ci-Cs- cyl, -0R ' ₃ group, wherein R' is hydrogen or -CC-alkyl, and

n is a number from 1 to 50

For the purposes of the present invention, compounds which belong to group (d) of the sterically hindered amines and are selected from: Uvinul 4049 H (from BASF Aktiengesellschaft); Uvinul® 4050 H (from BASF Aktiengesellschaft); Uvinul® 5050 H (from BASF Aktiengesellschaft); Tinu- vin ^® 123 (Ciba Specialty Chemicals.); Tinuvin®144 (from Ciba Specialty Chemicals); Lowilite 76 (Great Lakes Chemical Corporation); Lowilite® ^® 62 (from Great Lakes Chemical Corporation.); Lowilite® 94 (Great Lakes Chemical Corporation); Chimassorb® 119 (from Ciba Specialty Chemicals); Cyεorb® UV 3529 (Cytec); Cyasorb ^® UV 3346 (Cytec.); the compound of formula (XXXV) -1:

HN-CH _j 0- ₂ OH

N N

poly-methylpropyl-3-oxy- [4- (2,2,6, 6-tetramethyl) piperidinyl] siloxane, commercially available under the brand name UVASIL® 299

(Great Lakes Chemical Corporation); poly-methylpropyl-3-oxy-

[4- (1,2,2,6, 6-pentamethyl) piperidinyl] siloxane.

The compounds of group (d) of the sterically hindered amines which are used according to the invention have an average molecular weight M _n of 500 to 10,000, in particular 1,000 to 10,000.

At least one compound selected from the group consisting of chromans can also be contained in the stabilizer mixtures as optional component (s). These compounds preferably correspond to the formula (XXV)

wherein

R _{'19 is} hydrogen; -CC ₄ alkyl; C -C ₂ cycloalkyl; mono- or polyunsaturated C ₂ -C ₄ alkenyl; and

R ' ₂ o, R' ₂ ι, R ' ₂ and R' ₂₃ independently of one another hydrogen; -CC ₂₄ alkyl; C ₃ -C ₂ cycloalkyl; mono- or polyunsaturated C -C ₂₄ alkenyl; Carboxyl groups COOR _'19 ; Succinyl groups -CH (COOR _'19 ) -CH ₂ -COOR' _i9

mean. Possible C ₂₄ alkyl, C _{3 2} cycloalkyl and C ₂₄ alkylene radicals have already been listed as examples above. May be mentioned here again for:

-C-C ₂₄ alkyl groups methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert. -Butyl, pentyl, isopentyl, weopentyl, tert. -Pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl, octadecyl, octadecyl (The above terms isooctyl, isononyl, isodecyl and isotridecyl are trivial names and come from the alcohols obtained after oxosynthesis - see Ullmann's Encyclopedia of Industrial Chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11, pages 435 and 436);

C ₃ -C ₂ cycloalkyl groups, which are optionally substituted, cycloheptyl, cyclooctyl, cyclohexyl, cyclopentyl, methylcyclohexyl and its corresponding isomers;

C -C ₂₄ alkenyl groups vinyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4 - and 5-hexenyl.

Particularly preferred compounds of component (e) are 2,5,7,8-tetramethyl .2. (4 ', 8', 12 '-trimethyltridecyl) -chroman-6-ol (α-tocopherol), 2,5, 8-trimethyl .2. (4 ', 8', 12 '-trimethyltridecyl) -chroman-6-ol (ß-tocopherol), 2, 7, 8-trimethyl. 2- (4', 8 ', 12' - trimethyltridecyl) -chroman- 6-ol (γ-tocopherol), 2, 8-dimethyl. 2. - (4 ', 8', 12 'trimethyltridecyl) -chroman-6-ol (δ-tocopherol), 3, 4-di-hydro-2, 2,5,7, 8-pentamethyl-2H-l-benzopyran -6-ol and 6-hydroxy- 2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox).

As an optional component (f) calcium, magnesium, cerium, iron and manganese salts can be used in the stabilizer mixtures of at least selected one organic ^'or inorganic salt from the group consisting of zinc, may be included.

In the case of cerium, iron and manganese salts, the oxidation level +2 of iron and manganese and +3 of cerium is important.

Preferred organic salts of zinc, calcium, magnesium, iron (II) and manganese (II) correspond to the formula Me (An) ₂ , preferred organic salts of cerium (III) to the formula Ce (An) ₃ , where Me is for zinc, calcium , Magnesium, iron (II) or manganese (II) and An stands for an anion of an organic acid or an enol. The acid can be linear or branched, saturated or unsaturated, aliphatic, aromatic, araliphatic or cycloaliphatic and optionally also substituted by hydroxyl or alkoxyl groups. The acid preferably contains one to 24 carbon atoms. Such organic acids are, for example, sulfonic acids, sulfinic acids, phosphonic acids or phosphinic acids, preferably carboxylic acids.

Examples of carboxylic acids of this type are formic acid, vinegar, propion, butter, iosobutter, capron, 2-ethyl capron, caprylic, capric, lauric, palmitic, stearic, behen, oil, Milk, Rizolinolein, 2-Ethoxypropion-, Benzoe-, Salicyl-, 4-Butylbenzoe-, 2-, 3- or 4-Toluyl-, 4-Dodecylbenzoe-, Phenylessig-, Naphthyles- sig-, Cyclohexancarbon- , 4-butylcyclohexane carbonic and cyclohexy less acetic acid. The carboxylic acid can also be used as a technical mixture of carboxylic acids, for example of fatty acids or of alkylated benzoic acids.

Examples of organic acids which contain sulfur or phosphorus are methanesulfonic, ethanesulfonic, dodecanesulfonic, benzenesulfonic, toluenesulfonic, 4-nonylbenzenesulfonic, benzenesulfonic or naphthalenesulfonic acid, dodecanesulfonic, benzenesulfonic or naphthalenesulfonic acid, butylphosphonic acid, butylphosphonic acid, butylphosphonic acid and their monoalkyl esters and diphenylphosphinic acid.

If An is an enolation, it is preferably an anion of a β-dicarbonyl compound or an o-acylphenol. Examples of β-dicarbonyl compounds are acetylacetone, benzoylacetone, dibenzoylmethane, methyl acetoacetate, ethyl acetoacetate, butyl acetoacetate, laurate acetoacetate and α-acetylcyclohexanone. Examples of o-acylphenols are 2-acetylphenol, 2-butyroylphenol, 2-acetylnaphthol, 2-benzoylphenol or salicylic aldehyde. The enolate is preferably the anion of a β-dicarbonyl compound with 5 to 20 carbon atoms.

Organic salts of zinc, calcium, magnesium, iron (II), manganese (II) and cerium (III) preferably contain as an anion acetylacetonate or an aliphatic monocarboxylate with, for example, 1 to 24 carbon atoms. Magnesium acetate, laurate and stearate, zinc formate, acetate, onanthate, laurate and stearate, calcium acetate, laurate and stearate, manganese acetate, laurate and stearate, zinc acetylacetonate, calcium acetylacetonate, magnesium acetylacetonate and Manganese acetylacetonate are some of the most preferred salts.

The inorganic salts of zinc, calcium, magnesium, iron (II), manganese (II) and cerium (III) are preferably their oxides, hydroxides, carbonates and magnesium or natural or synthetic dolomite or hydrotalcite. The inorganic salts are used as fine powders with average particle sizes of a few μm, preferably a few nm.

The stabilizer mixtures according to the invention are outstandingly suitable for stabilizing organic polymers against the negative influence of oxygen, heat and / or

Light. Examples of organic polymers which can be stabilized by the stabilizer mixtures are:

1. Polymers from monoolefins and diolefins, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene,

Polyisoprene or polybutadiene; also polymers from cycloolefins, such as polycyclopentene or polynorbones; polyethylene len (which may optionally be networked) such as HDPE, HDPE-HMW, HDPE-UHMW, MDPE, LDPE, LLDPE, BLDPE, VLDPE and ULDPE;

The polyolefins, such as those based on the aforementioned mono-olefins, preferably polyethylene and polypropylene, can have been prepared by all processes known from the literature, in particular according to the following processes:

(a) radical polymerization (generally carried out at high pressures and temperatures);

(b) catalytic polymerization using catalysts which are usually one or more metals from groups IVB, VB, VIB or VIII (groups 4, 5, 6 or

8/9/10 according to IUPAC) of the periodic table. These metals generally have one or more ligands, e.g. Oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, where the ligands can be π- or σ-coordinated. The metal complexes can in turn be present in free or supported form on substrates; For example, activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide can be mentioned as catalysts. Said catalysts can be both soluble and insoluble in the polymerization medium, and of course they are insoluble in the supported case. The catalysts can be used alone or in the presence of other activators, e.g. Metal alkyls, metal hydrides, halides or oxides of metal alkyls or metal alkyloxanes (are they correct? What kind of compounds are they?), The metals of these activators belonging to groups IA, ILA and / or IIIA (groups 1, 2 or 13 according to IUPAC) belong to the periodic table. These activators can be easily modified with other ester, ether, amine or silyl ether groups. These catalytic systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or "single site catalyst" (SSC) catalysts.

2. Mixtures of polymers as described under point 1, such as mixtures of polypropylene with polyisobutylene; Mixtures of polypropylene with polyethylene, for example PP / HDPE, PP / LDPE); Mixtures of different types of polyethylene, for example LDPE / HDPE. 3. Copolymers of monoolefins and diolefins with one another or with other monomers containing vinyl groups. Examples of such copolymers are ethylene / propylene copolymers, LLDPE and its blends with LDPE, propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / Methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate Copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbones; likewise mixtures of the copolymers mentioned with one another or with the polymers listed under point (1),

^; such as polypropylene / ethylene / propylene copolymers, LDPE / ethylene / vinyl acetate (EVA) copolymers, LDPE / ethylene / acrylic acid (EAA) copolymers, LLDPE / EVA, LLDPE / EAA and alternating or statistical polyalkylene / carbon monoxide Copolymers and their blends with other polymers, such as polyamides.

4. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

5. Copolymers of styrene or α-methylstyrene with dienes or acrylic acid derivatives, such as styrene / butadiene, styrene /

Acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; Mixtures of high impact strength between styrene copolymers and other polymers, such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers, block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, Styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

6. graft copolymers of styrene or α-methylstyrene, such as styrene in polybutadiene, styrene in polybutadiene / styrene or polybutadiene / acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; Styrene, acrylonitrile and methyl methacrylate in polybutadiene; Styrene and maleic anhydride in polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; Styrene and maleimide in polybutadiene; Styrene and alkyl acrylates or alkyl methacrylates in polybutadiene; Styrene and acrylonitrile in ethylene / propylene / diene terpolymers, styrene and acrylonitrile in polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers, and also mixtures of copolymers listed under point (5), such as mixtures of known copolymers such as ABS, MBS, ASA or AES.

5 7. Halogen-containing polymers, such as polychloroprene, chlorinated elastomers, chlorinated or brominated isobutylene / isoprene copolymers (“halobutyl rubber”), chlorinated or chlorosulfonated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride or polyvinylidene fluoride; likewise their copolymers, for example based on vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate.

15

Polymers derived from oc, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.

20

9. Copolymers based on monomers from item (8) with one another or with other unsaturated monomers, such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkylacrylate copolymers or acrylic

25 nitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

10. Polymers derived from unsaturated alcohols and amines or their acyl or acetal derivatives, such as polyvinylal

30 alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; likewise their copolymers with the olefins listed under point (1).

35 11. Homopolymers and copolymers of open-chain or cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers of the compounds described above with bisglycidyl ethers.

40 12. Polyacetals, such as comonomers containing polyoxymethylene and polyoxymethylene, for example ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

45 13. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides. 14. Polyurethanes derived from hydroxy-terminated polyethers, polyesters or polybutanes serve on the one hand and aliphatic or aromatic polyisocyanates on the other hand and their respective precursor compounds.

5

15. Polyamides and copolyamides, derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic

10 polyamides starting from m-xylene diamine and adipic acid; Polyamides starting from hexamethylenediamine and isophthalic and / or terephthalic acid and with or without an elastomer as modifier, such as poly-2, 4, 4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; also block copolymers

15 of the above polyamides with polyolefins, olefinic copolymers, ionomers or elastomers, chemically bound or grafted, or with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; likewise polyamides or copolyamides modified with EPDM or ABS and

20 polyamides condensed during processing ("RIM polyamide system").

16. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzoimidazoles.

25

17. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1, dimethylolcyclohexane terephthalate and polyhydroxybene.

30 zoates, also block copolyether esters, which are derived from polyethers with hydroxyl-terminated groups, and polyesters modified with polycarbonates or MBS.

18. Polycarbonates and polyester carbonates. 35

19. Polysulfones, polyether sulfones and polyether ketones.

20. Crosslinked polymers, which are derived on the one hand from aldehydes and on the other hand from phenols, urea and melamines

40 are such as phenol / formaldehyde, urea / formaldehyde and melamine / formaldehyde resins.

21. Dried and undried alkyd resins.

45 22. Resins based on unsaturated polyesters, which are derived from copolyesters of saturated and unsaturated carboxylic acids with polyhydric alcohols and vinyl compounds as a crosslinker, as well as the above-mentioned halogen-containing flame-resistant resins.

23. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.

24. alkyd resins, resins based on polyesters or acrylated resins crosslinked with melamine, resins based on urea,

10 resins based on isocyanates, resins based on isocyanates, resins based on polyisocyanates or epoxy resins.

25. Crosslinked, derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds

15 epoxy resins, such as products from diglycidyl ethers of bis ^; phenol A and bisphenol F, which are crosslinked with conventional crosslinkers, such as anhydrides or amines in the presence or absence of accelerators.

20 26. Naturally occurring polymers such as cellulose, rubber,

Gelatin and its derivatives which have been chemically modified to obtain homologous polymers, such as cellulose acetates, propionates and butyrates, or cellulose ethers such as methyl cellulose; likewise hydrocarbon resins ("rosins") and their

25 derivatives.

27. Mixtures of the stated polymers (“polyblends”), such as PP / EPDM, polyamides / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM /

30 • thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, POM / MBS, PPO / HIPS, PPO / PA.6.6 and copolymers, PA / HDPE, PAPP, PAPPO, PBT / PC / ABS, PBT / PET / PC. ..

28. Natural or synthetic organic materials, which are 35 pure monomeric compounds and their mixtures, such as mineral oils, animal or vegetable oils, fats or waxes, oils, fats or waxes based on synthetic esters, e.g. Phthalates, adipates, phosphates and trimellitates, as well as mixtures of synthetic esters with mineral oils in any weight ratio, as well as aqueous emulsions of the organic materials mentioned.

29. Aqueous emulsions based on natural or synthetic rubbers, such as natural latex or latices

45 carboxylated styrene / butadiene copolymers. The stabilizer mixtures according to the invention can also be used in the production of polyurethanes, in particular in the production of polyurethane foams. The polyurethanes and polyurethane foams obtained in this way are thereby protected against the negative influences of oxygen, heat and / or light.

The polyurethanes can be obtained, for example, by reacting polyethers, polyesters and polybutadienes which contain terminal hydroxyl groups with aliphatic or aromatic polyisocyanates.

Polyethers with terminal hydroxyl groups are generally known and can be produced, for example, by polymerizing epoxides, e.g. Ethylene oxide, propylene oxide, butylene oxide, styrene oxide or epichlorohydrin, for example in the presence of boron trifluoride or by addition reaction of the epoxides, alone or in a mixture with one another, or in a subsequent reaction with starters which contain reactive hydrogen atoms, such as water, alcohols, ammonia or amines such as ethylene glycol, propylene-1, 2- or -1, 3-glycol, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Polyethers containing sucrose can also be used. In most cases, polyethers with a large number of primary 0H groups (up to 90% of the total 0H groups present in the polyether) are preferred. In addition, polyethers modified with vinyl polymers can be used, which are produced, for example, by polymerizing styrene and acrylonitrile in the presence of polyethers which are polybutadienes with OH groups.

The aforementioned compounds are polyhydroxy compounds and have molecular weights in the range from 400 to 10,000 g / mol, in particular from 800 to 10,000 g / mol, preferably from 1,000 to 6,000 g / mol, accordingly the polyethers accordingly have at least 2, usually 2 to 8, but preferably 2 to 4 hydroxyl groups and are known for the production of homogeneous polyurethanes and cellular polyurethanes.

Mixtures of the abovementioned compounds which have at least two hydrogen atoms reactive toward isocyanate groups and preferably have a molecular weight of 400 to 10,000 g / mol can of course also be used.

Suitable are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cy- clohexane-1, 3- and -1, 4-diisocyanate and mixtures of these isomers; l-isocyanate-3, 3, 5-trimethyl-5-isocyanatmethylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate and mixtures of these isomers; Hexahydro-1, 3- and / or -1, 4-phenylene diisocyanate, perhydro-2,4'- and / or -4, 4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4 - And 2, 6-tolylene diisocyanate and mixtures of these isomers; Diphenylmethane-2, 4 '- and / or -4, 4' -diisocyanate, naphthylene-1, 5-diisocyanate, triphenylmethane-4, 4 ', 4 "-triisocyanate, polyphenylpolymethylene polyisocyanates, obtained by aniline / formaldehyde condensation of phosgenation, m- and p-isocyanate phenylsulfonyl isocyanates, perchlorinated aryl polyisocyanates, polyisocyanates containing carbodiimide groups, polyisocyanates containing allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing urethane groups, acylated urea groups, containing urea groups Polyisocyanates containing biuret groups, polyisocyanates containing ester groups, the reaction products of the above-mentioned isocyanates with acetals and polyisocyanates which contain residues of polymeric fatty acids.

Furthermore, it is also possible to use distillation residues which contain isocyanate groups, these residues being present as such or dissolved in one or more of the above-mentioned polyisocyanates and being obtained during the industrial production of isocyanates. It is also possible to use any mixtures of the above-mentioned polyisocyanates.

Industrially accessible polyisocyanates which are easily accessible are preferably used, examples of which are about 2,4- and -2, 6-tolylene diisocyanate and any mixtures of these isomers (“TDI”); Polyphenylpolymethylene polyisocyanates obtained by aniline / formaldehyde condensation followed by phosgenation ("crude MDI"); Polyisocyanates containing carboimide, urethane, allophanate, isocyanurate, urea and / or biuret groups (so-called modified polyurethanes).

The organic polymers which can be stabilized by the stabilizer mixtures according to the invention are preferably natural, semisynthetic or synthetic polymers selected from the groups described above. In particular, the stabilizer mixtures according to the invention are used in the stabilization of thermoplastic polymers, preferably polyolefins, particularly preferably polyethylene and polypropylene or their copolymers with mono- and diolefins. Accordingly, the present invention further relates to non-living organic materials which contain an effective amount of a stabilizer mixture according to the invention, these materials in particular being organic polymers.

The present invention further relates to articles which have been produced from stabilized, non-living, organic materials according to the invention, these materials in turn being in particular organic polymers.

The stabilizer mixtures according to the invention are outstandingly suitable for preventing the degradation caused by oxygen, heat and / or light in the non-living, organic materials, in particular the organic polymers, and are therefore used as process stabilizers.

Components (a) and (b) and optionally (c) and / or (d) and / or (e) and / or (f) of the stabilizer mixtures according to the invention can be added either individually or in a mixture with one another. (In the following, instead of "non-living, organic materials, in particular the organic polymers", we simply speak of "materials to be stabilized")

Component (a) is the materials to be stabilized in an amount of 0.0005 to 5 wt .-%, preferably from 0.001 to 2 wt .-%, and in particular from 0.01 to 2 wt .-%, based on the weight of the materials to be stabilized.

Components (b) and optionally (c) and / or (d) and / or (e) and / or (f) are each added to the materials to be stabilized in an amount of from 0.01 to 10% by weight, preferably from 0 , 01 to 5 wt .-%, particularly preferably from 0.025 to 3 wt .-%, and in particular from 0.025 to 1 wt .-%, based on the weight of the materials to be stabilized.

If components (a) and (b) and, if appropriate, (c) and / or (d) and / or (e) and / or (f) of the stabilizer mixtures according to the invention are added as a mixture to the materials to be stabilized, they are corresponding to Quantities described above (based on the weight of the materials to be stabilized) in the stabilizer mixtures according to the invention.

In addition to components (a) and (b), preferred stabilizer mixtures also contain at least one compound selected from the group consisting of sterically hindered phenols as component (c) and optionally further compounds selected from the group of components (d), (e) and (f).

Further preferred stabilizer mixtures contain, in addition to components (a) and (b), at least one compound selected from the group consisting of sterically hindered amines as component (d) and, if appropriate, further compounds selected from the group of components (c), (e ) and (f).

In addition to components (a) and (b), further preferred stabilizer mixtures contain at least one compound selected from the group consisting of chromans as component (e) and, if appropriate, further compounds selected from the group consisting of components (c), (d) and (f). ,

Further preferred stabilizer mixtures contain, in addition to component (a) and (b), at least one organic or inorganic salt selected from the group consisting of zinc, calcium, magnesium, cerium, iron and manganese salts as component (f) and, if appropriate, also further compounds selected from the group of components (c), (d) and (e).

In addition to components (a) and (b), preferred stabilizer mixtures also contain at least one compound selected from the group consisting of sterically hindered phenols as component (c) and at least one compound selected from the group consisting of sterically hindered amines as component (d) and optionally further compounds selected from the group of components (e) and (f).

Further preferred stabilizer mixtures contain, in addition to component (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c) and at least one compound selected from the group of chromanes as component (e) and, if appropriate, still further compounds selected from the group of components (d) and (f).

In addition to components, further preferred stabilizer mixtures contain. (a) and (b) at least one compound selected from the group consisting of sterically hindered phenols as component (cj and at least one organic or inorganic salt selected from the group consisting of zinc, calcium, magnesium, cerium, Iron and manganese salts as component (f) and optionally further compounds selected from the group of components (d) and (e). Further preferred stabilizer mixtures contain, in addition to components (a) and (b), at least one compound selected from the group consisting of sterically hindered amines as component (d) and at least one compound selected from the group of chromanes as component (e) and, if appropriate, still further compounds selected from the group of components

(c) and (f).

Further preferred stabilizer mixtures contain, in addition to components (a) and (b), at least one compound selected from the group consisting of sterically hindered amines as component (d) and at least one organic or inorganic salt selected from the group consisting of zinc and calcium -, Magnesium, cerium, iron and manganese salts as component (f) and, if appropriate, further compounds selected from the group of components (c.) And (e).

In addition to components (a) and (b) and at least one compound selected from the group consisting of chromans as component (e) and at least one organic or inorganic salt selected from the group consisting of zinc, calcium, magnesium and other preferred stabilizer mixtures. , Cerium, iron and manganese salts as component (f) and optionally further compounds selected from the group of components (c) and (d).

Further preferred stabilizer mixtures contain, in addition to component (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), and at least one compound selected from the group consisting of sterically hindered amines as component

(d) and at least one compound selected from the group of chromanes as component (e) and optionally further compounds of component (f).

Further preferred stabilizer mixtures contain, in addition to component (a) and (b), at least one compound selected from the group consisting of sterically hindered phenols as component (c), and at least one compound selected from the group consisting of sterically hindered amines as component (d) and at least one organic or inorganic salt selected from the group consisting of zinc, calcium, magnesium, cerium, iron and manganese salts as component (f) and optionally further compounds of component (e). The stabilizer mixtures according to the invention can also contain further stabilizers (co-stabilizers) selected from the groups listed below.

1. Antioxidants

1.1 Alkylated monophenols, such as: 2, 6-di-tert. -butyl-4-methylphenol; 2-tert. -Butyl-4, 6-dimethylphenol; 2, 6-di- tert. -butyl-4-ethylphenol; 2,6-di-tert. -butyl-4-n-butylphenol; 2,6-di-tert. butyl-4-isobutylphenol; 2, 6-dicyclopentyl-4-methylphenol; 2- (α-methylcyclohexyl) -4, 6-dimethylphenol; 2, 6-dioctadecyl-4-methylphenol; 2, 4, 6-tricyclohexylphenol; 2,6-di-tert. butyl-4-methoxymethylphenol; Nonylphenols with linear or branched alkyl chains, such as 2,6-dinonyl-4-methylphenol; 2,4-dimethyl-6- (1 '-methylun ^{ι "} dec-1' -yl) phenol; 2,4-dimethyl-6- (1'-methylheptadec-1 '-yl) phenol; 2,4 -Dimethyl-6- (1 '-methyltridec-1' -yl) phenol; and their mixtures.

1.2 alkylthiomethylphenols, such as: 2, 4-dioctylthiomethyl-6-tert. -butylphenol; 2,4-dioctylthiomethyl-6-methylphenol; 2,4-dioctylthiomethyl-6-ethylphenol; 2,6-didodecyl-thiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkylated hydroquinones, such as:

2,6-di-tert. -butyl-4-methoxyphenol; 2,5-di-tert. -butylhydroquinone; 2,5-di-tert. -amylhydrochinon; 2,6-diphenyl-4-octadecyloxyphenol; 2,6-di-tert. -butylhydrochinon; 2,5-di-tert. -butyl-4-hydroxyanisole; 3, 5-di-tert. -butyl-4-hydroxyanisole; 3, 5-di-tert. -butyl-4-hydroxyphenyl; Bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 Tocopherols, such as: α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and their mixtures (vitamin E).

1.5 hydroxylated thiodiphenyl ethers such as: 2,2'-thio-bis (6-tert-butyl-4-methylphenol); 2,2 'thio-bis (4-octylphenol); 4,4 'thio-bis (6-tert-butyl-3-methylphenol);

4,4 'thio-bis (6-tert-butyl-2-methylphenol); 4,4'-thio-bis (3,6-di-sec-amylphenol); 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6 alkylidene bisphenols such as: 2,2'-methylene-bis (6-tert-butyl-4-methylphenol); 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol); 2,2 'methylene bis [4-methyl-6- (α-methylcyclohexyl) phenol]; 2,2 'methylene bis (4-methyl-6-cyclohexylphenol); 2,2 'methylene bis (6-nonyl-4-methylphenol); 2.2 '-Me- ethylene bis (4,6-di-tert-butylphenol); 2,2'-ethylidene bis (4,6-di-tert-butylphenol); 2,2 'ethylidebis (6-tert-butyl-4-isobutylphenol); 2,2'-methylene-bis [6-α-methylbenzyl) -4-nonylphenol]; 2,2'-methylene-bis [6- (α, -dimethylbenzyl) -4-nonylphenol]; 4,4'-methylene-bis (2,6-di-tert-butylphenol); 4,4 'methylene bis (6-tert-butyl-2-methylphenol); 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane; 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol; 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane; 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane; Ethylene glycol bis [3,3- bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate]; Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene; Bis [2- (3 '- tert -butyl-2' -hydroxy-5 '-methylbenzyl) -6-tert. -butyl-4-methylphenyl] terephthalate; 1, 1-bis (3,5-dimethyl

'2-hydroxyphenyl) butane; 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane; 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane; 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7 Benzyl compounds containing oxygen, nitrogen or sulfur, such as: 3, 5, 3 ', 5' tetra-tert. -butyl-4, 4'-dihydroxydibenzyl ether; Octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate; Tridecyl-4-hydroxy-3,5-di-tert. -butyl-benzyl-mercaptoacetate; Tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine; Bis (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate; Bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide; Iso-octyl-3, 5-di-tert. -butyl-4-hydroxybenzylmercaptoacetate.

1.8 Hydroxybenzylated malonates such as: dioctadecyl-2,2- bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate; Dioctadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate; Didodecyl mercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate; Bis [4- (1, 1, 3, 3-tetramethylbutyl) phenyl] - 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9 Aromatic hydroxybenzyl compounds, such as:

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene; 1,4-bis (3,5-di-tert-butylhydroxybenzyl) -2,3,5,6-tetramethylbenzene; 2, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10 triazine compounds such as: 2,4-bis (octylmercapto) - 6- (3,5-di-tert-butyl-4-hydroxyaniline) -1,3,5-triazine; 2-0c-tylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyaniline) - 1,3,5-triazine; 2-0ctylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine; 2,4,6-tris (3,5-di-tert.- butyl-4-hydroxyphenoxy) -1,2,3-triazine; 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate; 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate; 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine; 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexa- hydro-1,3,5-triazine; 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11 benzyl phosphonates such as: dimethyl-2, 5-di-tert. -butyl-4-hydroxybenzylphosphonate; Diethyl-3, 5-di-tert. -butyl-4-hydroxybenzylphosphonate; Dioctadecyl-3, 5-di-tert. -butyl-4-hydroxybenzylphosphonate; Dioctadecyl-5-tert. -butyl-4-hydroxy-3-methylbenzylphosphonate; Calcium salts of the monoethyl esters of 3, 5-di-tert. -butyl-4-hydroxybenzylphosphonic acid.

1.12 acylaminophenols such as: 4-hydroxylauranilide; 4-hydroxystearanilide; Octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13 esters of ß- (3,5-di-tert-butyl-4-hydroχyphenyl) propionic acid with mono- or polyhydric alcohols, such as: methanol, ethanol, n-octanol, isooctanol, 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 -Thioundecanol, 3-thiopentadecanol, triethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

1.14 esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as: methanol, ethanol, n-octanol, isooctanol, 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 -Thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

1.15 esters of β- (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as: methanol, ethanol, n-octanol, isooctanol, 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 -Thioundecanol, 3-thiopenta- decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

1.16 esters of (3, 5-di-tert-butyl-4-hydroxyphenyl) acetic acid with mono- or polyhydric alcohols, such as: methanol,

Ethanol, n-octanol, isooctanol, 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-thioundecanol, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane.

1.17 amides of ß- ^' (3, 5-di-tert-butyl-4-hvdroχyphenyl) propionic acid, such as: N, N' -bis (3, 5-di-tert-butyl-4-hydroxy - phenylpropionyl) hexamethylenediamide; N, N 'bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamide; N, N '- bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide; N, N '- bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxalmide (Naugard® XL-1 from Uniroyal).

1.18 Ascorbic acid and derivatives such as vitamin C and palmitola corbate.

1.19 amine antioxidants such as: N, N '-di-isopropyl-p-phenylenediamine; N, N '-di-sec-butyl-p-phenylenediamine; N, N'-bis (1,4-dimethylpentyl) p-phenylenediamine; N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine; N, N '-Bis (1-methylheptyl) -p-phenylenediamine; N, N '-dicyclohexyl-p-phenylenediamine; N, N'-diphenyl-p-phenylenediamine; N, N '-Bis (2-naphthyl) -p-phenylenediamine; N-isopropyl-N'-phenyl-p-phenylenediamine; N- (1,3-dimethylbutyl) - '-phenyl-p-phenylenediamine; N- (1-methylheptyl) - '-phenyl-p-phenylenediamine; N-cyclohexyl-N '-phenyl-p-phenylenediamine; 4- (p-toluenesulfamoyl) diphenylamine; N, N '-Dirnethyl-N, N'- di-sec. butyl-p-phenylenediamine; diphenylamine; N-allyl diphenyl lamin; 4-isopropoxydiphenylamine; N-phenyl-1-naphthylamine; N- (4-tert-octylphenyl) -1-naphthylamine; N-phenyl-2-naphthyla-in; Dioctylphenylamines such as p, p '- (di-tert-octylphenyl) amine; 4-n-butylaminophenol; 4-butyrylaminophenol; 4-nonanoylaminophenol; 4-dodecanoylaminophenol; 4-0ctadecanoylaminophenol; Bis (4-methoxyphenyl) amine; 2,6-di-tert. -butyl-4-dimethylamino-methylphenol; 2,4 '-diamino-diphenylmethane;4,4'-diaminodiphenylmethane; N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane; 1,2-bis [(2-methylphenyl) amino] ethane; 1,2-bis (phenylamino) propane; Bis [4- (1 ', 3' -dimethylbutyl) phenyl] amine; Mixtures of mono- and dialkylated tert-butyl / tert-octyl diphenyla ines; Mixtures of mono- and dialkylated nonyldiphenylamines; Mixtures of mono- and dialkylated dodecyldiphenylamms; Mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines; Mixtures of mono- and dialkylated tert. -Butyldiphenylamine; 2, 3-dihydro-3, 3-dimethyl-4-ϊ-l, 4-benzothiazine; phenothiazine; Mixtures of mono- and dialkylated tert. -Butyl / tert. -Octylphenothiazines; Mixtures of mono- and dialkylated tert. -Octylphenothiazinen; N-allylphenothiazine; N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene; N., N-bis (2,2,6, 6-tetramethyl-piperidin-4-yl) hexamethylene diamine; Bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate; 2,2,6, 6-tetramethylpiperidin-4-one; 2,2,6, 6-tetramethylpiperidin-4-ol.

1.20 benzofuranones and indolinones, such as: those described in US 4,325,863, US 4,338,244, US 5,175,312, US

^; 5,216,052, US 5,252,643, DE 43 16 611 AI, DE 43 16 622 AI, DE 43 16 876 AI, EP 589 839 AI and EP 591 102 AI disclosed compounds, 3- [4- (2-acetoxyethoxy) phenyl] -5, 7-di-tert. -butylbenzofuran-2-one, 3- [4- (2- (stearoyloxyethoxy) phenyl] -5, 7-. di-tert-butylbenzofuran-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- on, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7-di-tert-butylbenzofuranone-2-one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl) -5, 7-di-tert-butylbenzofuran-2-one, in particular the compound of the formula

2. UV and light stabilizers

2.1 Derivatives of 2- (2 '-hydroxyphenbenztriazoles, such as: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl ) benzotriazole; 2- (5'-tert-butyl-2'-hydroxyphenyl) benztriazole; 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 'octyloxyphenyl) benzotriazole; 2- (3', 5 '-di - tert -amyl-2'-hydroxyphenyl) benzotriazole; 2- [3 ', 5' -Bis (α, α-di- methylbenzyl) -2'-hydroxyphenyl] benzotriazole; 2- [3 't. -Butyl-2 '-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3 '-ter. -Butyl-5 '- (2- (2-ethylhexyloxy) carbonylethyl) -2'-hydroxyphenyl] -5-chlorobenztriazole, 2 [3' -ter. - Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole, 2- [3' -ter. -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; 2- [3 't. -Butyl-2 '-hydroxy- 5' - (2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2, 2 '-methylene-bis [4- (1, 1, 3, 3-tetramethylbutyl) -6-benzotriazol-2-yl - phenol]; the fully esterified product of 2- [3 '-tert. -Butyl- 5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole ^c with polyethylene glycol 300; [R-CH ₂ CH ₂ -C0o (CH ₂ ) ₃ -] with R equal to 3 'tert. -Butyl-4-hydroxy-5 '-2Jϊ-benzotriazol-2-ylphenyl; 2- [2 '-hydroxy-3' - (α, α-dimethylbenzyl) -5 '- (1,1,3, 3-tetramethylbutyl) phenyl] benzotriazole; 2- [2 '-Hydroxy-3' - (1,1,3, 3-tetramethylbutyl) -5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2 derivatives of 2-hydroxybenzophenones, such as: 4-hydroxy-; 4-methoxy-; 4-octyloxy; 4-decyloxy; 4-dodecyloxy; 4-benzyloxy; 4, 2 ', 4' -Trihydroxy-; 2'-Hydroxy-4,4'-dimethoxy-2-hydroxybenzophenone.

2.3 Optionally substituted esters of benzoic acid, such as: phenyl salicylate, 4-tert. Butylphenyl salicylate, octyl phenyl salicylate, benzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, dibenzoyl resorcinol, 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-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert. -butylphenyl-3, 5-di-tert. butyl 4-hydroxybenzoate.

2.4 acrylates, such as: ethyl or isooctyl-α-cyano-β, β-diphenyl acrylate; Methyl-α-carbomethoxycinnamate, methyl or butyl-α-cyano-ß-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate, N- (ß-carbomethoxy-ß-cyanovinyl) - 2-methylindoline ,

2.5 Nickel compounds, such as: nickel complexes from

2, 2 '-thio-bis [4- (1,1, 3, 3-tetramethylbutyl) phenol], for example 1: 1 or 1: 2 complexes, with or without additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3, 5-di-tert. -butylbenzylphosphonic acid, such as such as methyl or ethyl esters, nickel complexes with ketoximes, such as 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

2.6 Other sterically hindered amines and their N-alkoxy derivatives, such as: poly-methylpropyl-3-oxy [4- (2,2,6, 6-tetra-methyl) piperidinyl] siloxane, polymethylpropyl-3-oxy- [ 4- (1, 2, 2, 6, 6-pentamethyl) piperidinyl] siloxane, the condensation product of 1- (2-hydroxyethyl) -2, 2, 6, 6-tetra-4-hydroxy-piperidine and succinic acid; the condensation product, linear or cyclic, of N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidinyl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-l, 3, 5-s-triazines; Tris (2, 2, 6, 6-tetrame-

^; thyl-4-piperidinyl) nitrilotriacetate; Tetrakis (2, 2, 6, 6-tetra-methyl-4-piperidinyl) -1, 2, 3, 4-butanetetracarboxylate; 1, 1 '- (1, 2-ethanediyl) bis (3,3,5, 5-tetramethylpiperazinone; 4-benzoyl-2, 2, 6, 6-tetramethylpiperidine; 4-stearyloxy-2, 2, 6 , 6-tetramethylpiperidine; bis (1, 2, 2, 6, 6-pentamethylpiperidinyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate; Bis (l-octyloxy-2, 2,6, 6-tetramethylpiperidinyl) succinate; the condensation product, linear or cyclic, from N, N'-bis (2,2,6, 6-tetramethyl-4-piperidinyl) hexamethylene - diamine and 4-morpholine-2, 6-dichloro-l, 3, 5-triazine; the condensation product of 2-chloro-4, 6-di- (4-n-butylamino-2, 2,6, 6 -tetramethylpiperidinyl) -1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane; the condensation product from 2-chloro-4, 6-di- (4-n-butylamino-l, 2.2, 6,6-pentamethylpiperidinyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3 , ^' 8-triaza-spiro [4.5] decane-2,4-dione; 3-dodecyl-l- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione; 3-dodecyl -l- (1, 2,2,6,6-pentamethyl-4-piperidinyl) pyrrolidin-2,5-dione; a mixture of 4-hexadecyloxy and 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidine; the condensation product of NN'-bis (2, 2, 6, 6-tetra-methyl-4-piperidinyl) hexamethylene diamine and 4-cyclohexylamino-2, 6-dichloro-l, 3, 5-triazine; the condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine; 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]; N- (2, 2, 6, 6-tetramethyl-4-piperidi- nyl) -n-dodecylsuccinimide; N- (1, 2, 2, 6, 6-pentamethyl-4-piperidinyl) -n-dodecylsuccinimide; 2-undecyl-7, 7,9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxospiro [4.5] decane; the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3, 8-diaza-4-oxo-spiro [4.5] decane and epichlorohydrin; 1, 1-bis (1, 2, 2, 6, 6-pentamethyl-4-piperidinyloxycarbonyl) -2- (4-methoxyphenyl) ethene; the diester of 2-methoxymethylene malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine;

2.7 oxamides, such as: 4,4'-dioctyloxyoxanilide; 2,2 'diethox yoxanilide; 2,2'-dioctyloxy-5, 5'-di-tert. -butoxanilid;

2,2'-didodecyloxy-5, 5'-di-tert. -butyloxanilid;

2-ethoxy-2'-ethyloxanilide; N, N 'bis (3-dimethylaminopropyl) oxamide; 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mis

with 2-ethoxy-2'-ethyl-5, 4'-di-tert. -butoxanilid; and mixtures of disubstituted ortho- and para-methoxyoxanilides and mixtures of disubstituted ortho- and para-ethoxyoxanilides. ,

2.8 2- (2-hydroxyphenyl) -1, 3, 5-triazines such as:

2,4,6-tris (2-hydroxy-4-octyloxyphenyl) 1,3,5-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; 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine; 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-tiiazine; 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- [2-Hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- [2-Hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4, 6- bis (2, -di-methylphenyl) -1,3,5-triazine; 2- (2-hydroxy-4-tride-cyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- [2-hydroxy-4 (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine; 2- (2-hydroxy-4-hexyloxyphenyl) -4, 6-diphenyl-l, 3,5-triazine; 2- (2-hydroxy-4-methoxyphenyl) 4,6-diphenyl-1,5,5-triazine; 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine; 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-l, 3,5-triazine; 2- {2-Hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5- triazine. 3. "Metal deactivators", such as: N, N-diphenyloxamide, N-salicylic-N '-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3, 5-di- tert -butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-l, 2, 4-triazole, bis (benzylidene) oxallyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl nylhydrazide, N, N'-diacydylidoyl adipide N'-bis (salicyloyl) oxallyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldihydrazide.

4. Other phosphites and phosphonites, such as:

2,2 ', 2 "-Nitrilo [triethyl-tris (3,3', 5, 5 '-tetra-tert-butyl-1, 1'-biphenyl-2, 2'-diyl) -phosphite; 2- Ethylhexyl- (3, 3 ', 5, 5' -tetra-tert-butyl-1, 1 '-biphenyl-2, 2' -diyl) phosphite.

5. hydroxylamines, such as:, N-dibenzylhydroxylamine; N, N-diethylhydroxylamine; N, N-dioctylhydroxylamine; N, N -dilylhydroxylamine; N, N-ditetradecylhydroxylamine; N, N-dihexadecylhydroxylamine; N, N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylaamin; N, N-Dialkylhydroxylamine derived from hydrogenated tall amines.

6. Nitrones, such as: N-benzyl-α-phenylnitrone; N-ethyl-α-methyl nitrone; N-octyl-α-heptyl nitrone; N-lauryl-α-undecyl nitrone; N-tetradecyl-α-tridecyl nitrone; N-hexadecyl-α-pentadecylnitrone; N-octadecyl-α-heptadecyl nitrone; N-hexadecyl-α-heptadecyl nitrone; N-octadecyl-α-pentadecyl nitrone; N-heptadecyl-α-heptadecyl nitrone; N-octadecyl-α-hexadecyl; Nitron derived from hydrogenated tallamines.

7. Thiosnergistic agents such as: dilauryl thiodipropionate; Distearyl thiodipropionate.

8. Agents which are capable of destroying peroxides, such as: esters of β-thiodipropionic acid, such as the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc di-butyldithiocarbamate , Dioctadecyl disulfide, pentaerythritol tetrakis (ß-dodecylmercapto) propionate.

9. Polyamide stabilizers, such as: copper salts combined with compounds of iodine and / or phosphorus, salts of divalent manganese.

10. Basic costabilizers, such as: Mela in, polyvinyl- ^c pyrrolido, dicyanodia ide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, urethanes, alkali and alkaline earth metal salts of fatty acids with a high molecular weight, such as Calcium stearate, zinc stearate, magnesium stearate, magnesium behenate, sodium ricinolate, potassium palmitate, antimony pyrocatecholate, tin pyrocatecholate, zinc pyrocatecholate.

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

12. Fillers and reinforcers, such as: calcium carbonate, silicates, glass fibers, glass beads (spheres), talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour as well as powders and fibers of other natural products, synthetic fibers.

13. Other additives, such as: plasticizers, dyes, pigments, lubricants, emulsifiers, rheology aids, catalysts, lubricants, optical brighteners, flame retardants, antistatic aids, blowing agents. The above-mentioned stabilizers (costabilizers) can, if appropriate, be added to the materials to be stabilized in an amount of from 0.01 to 10% by weight, based on the weight of the materials to be stabilized.

The fillers and reinforcers described under point 12, e.g. Talc, calcium carbonate, mica or kaolin can optionally be added to the materials to be stabilized in an amount of 0.01 to 40% by weight, based on the weight of the materials to be stabilized.

The fillers and reinforcers described under point 12, e.g. Metal hydroxides, in particular aluminum hydroxide or magnesium hydroxide, can optionally be added to the materials to be stabilized in an amount of 0.01 to 60% by weight, based on the weight of the materials to be stabilized.

Carbon black as filler can optionally be added to the materials to be stabilized in an amount of 0.01 to 5% by weight, based on the weight of the materials to be stabilized.

Glass fibers as reinforcers can optionally be added to the materials to be stabilized in an amount of 0.01 to 20% by weight, based on the weight of the materials to be stabilized.

Mixtures containing phenolic antioxidants and secondary antioxidants, such as phosphites or phosphonites, are generally used as process stabilizers for organic polymers, e.g. Polyolefins used (for example, temperatures up to 280 ° C can occur during the processing of polyolefins, which requires a correspondingly effective process stabilization of these polymers). The stabilizer mixtures according to the invention even allow process stabilization at even higher temperatures of approximately 300 ° C.

Components (a) and (b) and any further components (c) and / or (d) and / or (e) and / or (f) are incorporated individually or mixed with one another and, if appropriate, with others Stabilizers (costabilizers) - in the materials to be stabilized according to methods known per se, for example before or during processing, or the stabilizer mixtures according to the invention are dissolved or suspended in a solvent or suspending agent and before or after the solvent or Suspending agent added to the materials to be stabilized. Masterbatches can also be produced on the basis of the stabilizer mixtures according to the invention. which contain the former in an amount of 2.5 to 25 wt .-%, based on the total weight of the masterbatch.

The stabilizer mixtures according to the invention, optionally in the presence of other stabilizers (costabilizers), can be added, for example, to the polymers to be stabilized after the polymerization, but also during the polymerization or before the crosslinking.

The stabilizer mixtures according to the invention, if appropriate in the presence of other stabilizers (costabilizers), can be added to the materials to be stabilized in pure form, but also in waxes, oils or polymers.

Stabilizer mixtures according to the invention, optionally in the presence of other stabilizers (costabilizers), which can be used in solution or melt, can also be sprayed into the materials to be stabilized. This spraying can advantageously be carried out using the steam used during the deactivation of the polymerization catalyst and together with the steam.

In the case of spherically polymerized polyolefins, it may be advantageous to add the stabilizer mixtures according to the invention, if appropriate in the presence of other stabilizers (costabilizers), by spraying them together.

The polymers stabilized according to the invention can be deformed in a wide variety of ways, for example as films, fibers, tapes, melt compositions, profiles or injection molded parts.

The present invention also includes a method for stabilizing non-living organic materials against the negative influence of oxygen, heat and / or light, which is characterized in that an inventive stabilizer mixture is added to the non-living organic materials in an effective amount.

Claims

claims

1. Stabilizer mixture containing

(a) at least one compound of the general formula (I)

in what mean

B is a bridge - (R ³ ) C = N- or -N = C (R ³ ) -;

R ² is L 'or a group - (R ₂ N) C = C (L') ₂ , where the two radicals R and L 'can each be the same or different;

L 'is -CN, -COR, COOR, -S0 ₂ R;

L is oxygen, = NR or sulfur; and

R ¹ , R ³ and R independently of one another are hydrogen; linear or branched C ~ C ₂₄ alkyl; linear or branched

C ₂ -C ₂₄ alkenyl; linear or branched C ₂ -C ₄ ~ alkynyl; linear or branched C ₂ -Cs alkoxyalkyl; optionally substituted C ₃ -C ₂ cycloalkyl; an optionally substituted, five- or six-membered heterocyclic radical which contains at least one heteroatom selected from the group consisting of oxygen, nitrogen and sulfur; optionally substituted C ₆ -C ₂₀ aryl;

(b) at least one compound selected from the group consisting of organic phosphites, organic phosphines and organic phosphonites;

(c) optionally at least one compound selected from the group consisting of sterically hindered phenols; (d) optionally at least one compound selected from the group consisting of sterically hindered amines;

(e) optionally at least one compound selected from the group consisting of chromanes; and

(f) optionally at least one organic or inorganic salt selected from the group consisting of zinc, calcium, magnesium, cerium, iron and manganese salts.

Stabilizer mixture according to Claim 1, in which the compounds of group (b) the organic phosphites, organic phosphines and organic phosphonites are selected from those of the general formulas (VI) to (XV):

-Y ¹ —P (VI)

R'l7

\

P- -R'l ₈ (XIII)

/

R'l ₇

R'l7 R '17

\ /

P- (XV);

/

R _'17 ^• R' 17

in what mean

n '2, 3 or 4;

p '1 or 2;

q '2 or 3;

r 'is an integer from 4 to 12; y '1, 2 or 3;

z 'is an integer from 1 to 6;

A 'for n' is 2 a C-Ci ₈ alkylene group; a C ₂ -C alkylene group which contains an oxygen or sulfur atom or an NR ' ₄ group; a group of the general formula:

a group of the general formula:

or

a phenylene group;

for n 'is 3 a group -C _r Η _2r ' -ι- / wherein r 'has the meaning given above; and

for n 'is 4 a group of the general formula

A "for q 'is 2 or 3 has the same meaning as A' for n 'is 2 or 3; B 'a single chemical bond; a group -CH ₂ -, -CHR ' ₄ - or -CR'ιR' ₄ -; a sulfur atom; a C ₅ -C ₇ cycloalkylidene; a cyclohexylidene substituted with one to four C ₄ alkyl groups in the 3-, 4- and / or 5-position;

B "optionally interrupted by NH, N (C -C ₂₄ alkyl), P (-C ₂₄ alkyl), oxygen or sulfur C ~ C ₃ o-alkylene; optionally by NH, N (-C ₂₄ alkyl) ), P (-C ~ C ₂₄ alkyl), oxygen or sulfur interrupted mono- or polyunsaturated C ₁ -C ₃ o-alkylidene, optionally by

NH, N (Cι-C ₂₄ alkyl), P (Cι-C ₂₄ alkyl), oxygen or sulfur interrupted C ₅ -C ₇ -cycloalkylidene; C ₆ -C ₄ arylene or C ₅ -C ₂₄ heteroarylene optionally substituted with -C ₂₄ alkyl, C ₃ -C cycloalkyl or Ci-Cis alkoxy;

D 'for p' is 1 is a methyl group; and

for p 'is 2 a group -CHOCH ₂ -;

E 'for y' is 1 a -C ~ C ₂₄ alkyl; a group -OR'i; or halogen;

for y 'is 2 a group -0-A "-0-, where A" has the same meaning as A' for n 'is 2; and

for y 'is 3 a group R' ₄ C (CH ₂ 0-) ₃ , N (CH ₂ CH ₂ 0-) ₃ ;

Q 'is a z' -valent radical of an alcohol or phenol which is in each case bound to the phosphorus atom via an oxygen atom;

R ', R' ₂ and R ' _{3 are} independently hydrogen; a

Group -COOR ' ₄ - or -CONR' ₄ R '₄; Cι-C ₂₄ alkyl, which contains an oxygen or sulfur atom or a group -NR ' ₄ -; C ₇ -Cg phenylalkyl; C ₃ -C ₂ cycloalkyl; phenyl or naphthyl optionally substituted with halogen or one to three -CC ₂₄ alkyl, C ₁ -C ₂₄ alkoxy or C ₇ -C ₉ phenylalkyl groups; or a group of the general formula:

wherein m 'represents an integer from 3 to 6;

R ' _{4 is} hydrogen; C ₁ -C ₂ alkyl; C ₃ -C ₁₂ cycloalkyl; C ₇ -C ₉ phenylalkyl;

R's and R ' _{6 are} independently hydrogen; -C ₆ alkyl; C ₅ -C ₆ cycloalkyl;

R ' ₇ and R' ₈

for q 'is 2 independently of one another C 1 -C ₄ alkyl or together a pentamethylene group;

for q 'is 3 each a methyl group;

R _{'14 is} hydrogen; Ci-Cg-alkyl; cyclohexyl;

R _{'15 is} hydrogen; a methyl group;

X 'and Y' are a single chemical bond; an oxygen atom;

Z 'is a single chemical bond; a methylene group; a group -C (R'i ₆ ) ₂ -; a sulfur atom;

R'ι ₆ is Cι-C ₆ alkyl;

R'i ₇ and R'i _{8 are} independently hydrogen; optionally interrupted by NH, N (-CC ₄ alkyl), oxygen or sulfur -CC ₄ alkyl; C ₇ -Cg phenylalkyl; mono- or polyunsaturated CC ₂₄ alkenyl; C ₂ -C ₂₄ alkynyl; C-Cg alkoxyalkyl; optionally substituted C ₃ -C ₂ cycloalkyl; optionally substituted Cs-C ₂₄ heteroaryl; optionally substituted C ₆ ~ Co aryl; CC ₃₀ -

arylalkyl; C ₂ -C ₄ alkoxy.

3. Stabilizer mixture according to claim 1 or 2, in which the compounds of group (c) of the sterically hindered phenols are selected from those of the general formula (XIX):

in what mean

Rl '-C ₄ alkyl;

n "is a number 1, 2, 3 or 4;

X "is a methylene group; or a group of the general formulas (XX) or (XXI)

0 II CH ₂ -CH ₂ -CY "(XX);

O

CH- _j -C II- -O — CH, -CH ₂ - (XXI)

wherein Y "represents an oxygen atom; or a group -NH-;

where X "corresponds

for n "is 1 of a group of the general formula (XX) in which Y" is bonded to R ₂ 'and R ₂ ' is C -C ₂ 4 -alkyl;

for n "is equal to 2 of a group of the general formula (XX) in which Y" is attached to R 'and R ₂ ' is a C ₂ -C ₂ alkylene group; a C4 -C ₂ alkylene group, which contains one or more oxygen or sulfur atoms, means; where in the case that Y "represents a group -NH-, R ₂ 'represents a single chemical bond; for n "is 3 a methylene group; a group of the general formula (XXI) in which the ethylene group is bonded to R 'and R ₂ ' a group of the formula (XXII)

for n "is 4 of a group of the general formula (XX) in which Y" is bonded to R and R ₂ 'corresponds to a C ₄ -C ₁₀ -AI-Kantetraylgruppe.

Stabilizer mixture according to one or more of Claims 1 to 3, in which the compounds of group (c) of the sterically hindered phenols are selected from those which have a sterically hindered phenol group of the general formulas (I ') or (I'a)

included, the variables R'i and R ' ₂ independently of one another having the previously given meaning.

Stabilizer mixture according to one or more of claims 1 to 4, in which the compounds of group (c) of the sterically hindered phenols are selected from those which have a sterically hindered phenol group of the general formulas (II ') or (Il'a)

included, where the variables mean

R'i and R ' ₂ independently of one another have the meaning given above;

m 0 or 1;

n 1, 2 or 3;

X linear or branched Ci-Cs-alkyl;

Y is hydrogen; Halogen; C 1 -C ₄ acyloxy; -C-C ₄ alkoxy; amino; a siloxane residue;

R 'is a linear or branched C 1 -C 8 alkylene group; or a group -L 'ι-C00-L' ₂ -, -L 'ι-COO-L' ₂ -S-L ' ₃ - or -L' -S-L ' ₃ -;

L'i, L 'and L' ₃ independently of one another are a linear or branched C ₃ -Cιo alkylene group.

Stabilizer mixture according to one or more of claims 1 to 5, in which the compounds of group (d) of the sterically hindered amines are selected from those which have at least one group of the general formulas (XXIII) or (XXIV) (XXIII)

contain what mean

G hydrogen; or a methyl group,

Gi and G are independently hydrogen; a methyl group; or together an oxygen atom.

Stabilizer mixture according to one or more of Claims 1 to 6, in which the compounds of group (e) of the chromanes are selected from those which have the general formula

correspond, ^• in what mean

R ' _{9 is} hydrogen; C -C ₂₄ alkyl; C ₃ -C ₂ cycloalkyl; mono- or polyunsaturated C ₂ -C ₄ alkenyl; and

'20 R'2i R'22 and R ' ₂ 3 are independently hydrogen; -CC ₂₄ alkyl; C ₃ -Ci ₂ ~ cycloalkyl; mono- or polyunsaturated C ₂ -C ₂₄ alkenyl; Carboxyl groups COOR _'19 ; Sucinyl groups -CH (COOR _'19 ) -CH ₂ -COO' ₁₉ .

8. Non-living organic materials containing an effective amount of a stabilizer mixture according to one or more of claims 1 to 7.

9. Articles which have been produced from stabilized, non-living, organic materials according to claim 8.

10. A method for stabilizing non-living, organic materials against the negative influence of oxygen, heat and / or light, characterized in that the stabilizing mixture according to one or more of claims 1 to 7 in an effective amount to the non-living, organic materials admits.