CS197282B2 - Process for the stabilisation of plastic materials - Google Patents

Description

The present invention relates to a process for stabilizing plastics using novel hydroxybenzyl malonate esters.

These are compounds of formula I

and their acid addition salts, wherein n is 1 or 2,

R „represents an alkyl group having 1 to 6 carbon atoms,

R _b represents an alkyl group having 1 to 6 carbon atoms,

R _c is C 1 -C 9 alkyl, phenyl, benzyl or phenylethyl,

R _d represents an alkyl group having 1 to 6 carbon atoms, or

R _c and R <| together are tetrainethyl or pentamethylene,

R _e represents hydrogen, C 1 -C 5 alkyl, alkenyl or C 3 -C 4 alkynyl. or a (C až-C ar) aralkyl group,

R _f is hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl, (C 7 -C 8) aralkyl, and

X represents oxygen or the group -NR-, where

R is hydrogen, C 1 -C 18 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl or aralkyl C 7 -C 9 group

R ¹ represents hydrogen, -O ', -OH, C 1 -C 12 alkyl, C 3 -C 4 alkenyl, pro / pargyl, benzyl or -CH ₂ -CH (OR ⁵ ) —R ⁴ , where

R ⁴ is hydrogen, methyl or phenyl, and

R ⁵ is hydrogen or a group. A-CO-, or the radical R ¹ is represented by a group

A — CO--, and in both cases, A is C1-C12alkyl, C2-C3 alkenyl, cyclohexyl, phenyl, benzyl, furthermore phenyl or phenylethyl which is substituted 2 (C 1 -C 4) alkyl and hydroxyl groups, furthermore, C 1 -C 12 alkylamino, C 2 -C 16 dialkylamino, anilino, C 1 -C 12 alkoxy, benzyloxy or phenoxy,

R ² is a hydroxybenzyl group of the formula II

in which

R ⁶ and R ⁷ are each independently C 1 -C 9 alkyl, C 7 -C 9 aralkyl or C 5 -C 8 cycloalkyl, and

R ⁸ is hydrogen or methyl, and

R ³ , when n = 1, is an alkyl group having 1 to 20 carbon atoms or one or two groups -OR ⁹ , -SR ¹⁰ , -CO-RU, -CN, -CjOjYR ¹² , -O-CjOjR ¹³ , -P (O) ^(OR14) _2, alkyl having 1 to 10 carbon atoms, where

R ⁹ represents a phenyl or C 6 -C 10 alkylphenyl, benzyl or cyclohexyl group,

R ¹⁰ represents a phenyl group or an alkylphenyl group of 6 to 10 carbon atoms,

R ¹¹ represents an alkyl group having 1 to 12 carbon atoms,

Y is oxygen or -NR- and R is as defined above,

R ¹² represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a group of formula III

in which

R ¹⁷ has the meaning given for R ¹ , and

R _a , R _b , R _c , R d, R _e , R f are as defined in formula I,

R ¹³ represents a C 1 -C 17 alkyl group, a C 5 -C 12 cycloalkyl group or a phenyl group or a C 7 -C 9 phenylalkyl group, the phenyl radical being optionally substituted by a C 1 -C 4 alkyl group and / or or a hydroxyl group,

R ¹⁴ is C 1 -C 8 alkyl, allyl or phenyl, and

X is as defined above,

R ³ is furthermore -O-, -S-, -SO 2 or -SO 2 - interrupted C 2 -C 22 alkyl, C 3 -C 18 alkenyl, C 3 -C 8 alkynyl, cycloalkyl (C až-C uhlíku) alkyl, (Cc-C alkyl) alkylcycloalkyl, (C až-C ar) cycloalkylalkyl, (C až-C 19) aralkyl or (C alky-C alky alky) alkyl group, phenyl or —OR ¹⁵ , wherein:

R ¹⁵ is C 1 -C 18 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, cycloalkyl. (C 5 -C 12) or (C 7 -C 9) aralkyl, or R ³ is furthermore a group -O-C 1 O ¹⁶ R ¹⁶ or a group -NH-C 1 O ¹⁶ R ¹⁶ , wherein:

R ¹⁶ represents a C 1 -C 12 alkyl group, a C 2 -C 3 alkenyl group, a cyclohexyl group, a phenyl group, a benzyl group, two C 1 -C 4 alkyl groups and a phenyl or phenylethyl substituted hydroxyl group; or the symbol R ³ represents a group of formula III or group IV

R18

CO — Y — R ¹⁹ /

—OH2 — C \

CO-Y-R 20 (IV) wherein

R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, a phenyl group, a cyclohexyl group, a C 3 -C 8 alkoxyalkyl group or one of the above-defined groups -O-C 1 -J-R ¹⁶ or -NH-C (O) R ¹⁶ or has any of the meanings given for R ² , and

R ¹⁹ and R ²⁰ are independently C 1 -C 5 alkyl or the radical of formula III, or when n is 2,

R ³ is a direct bond, an alkylene group having 1 to 20 carbon atoms, also one or two -O-, -S-, -SO2- or • -CO-O- interrupted alkylene group having 2 to 20 carbon atoms, aren- a C 8 -C 14 bis-alkylene group, a C 4 -C 8 alkenylene group or a C 4 -C 8 alkynylene group.

R _a , R _b and R _d can be straight or branched (C 1 -C 6) alkyl groups such as methyl, ethyl, propyl, butyl, isobutyl, isopentyl or n-hexyl.

R _c can be straight or branched (C 1 -C 9) alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, isopentyl, n-hexyl, 2-ethylhexyl, n-nonyl or isononyl.

R _e and R _f may be alkyl groups of up to 5 carbon atoms, wherein R _e preferably contains 1 carbon atom less than R _b and the position of R _c and R _f is replaceable. R _e and R _f may also be alkenyl or alkynyl, for example allyl, methallyl, 2-butenyl or propargyl, especially allyl, R _o and R ₍ may also be aralkyl, for example benzyl, phenylethyl or methylbenzyl group.

Preferably, the symbols R _a, R _b, R _c and R i is methyl and R _e and R _t is hydrogen.

R ¹ , R ¹⁶ and A in the meaning of C 1 -C 12 alkyl may be a primary alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n- decyl or n-dodecyl.

R &lt; ¹⁵ &gt; and R &lt; ¹⁵ &gt; as alkyl having up to 18 carbon atoms can additionally be, for example, tridecyl, hexadecyl or octadecyl.

R, R ¹ , R ¹⁵ , R ¹⁶ and A in the meaning of an alkenyl group may be, for example, an allyl, methallyl or butenyl group.

R @ 3 and R @ ¹⁵ as C3 -C4 alkynyl may be, for example, propargyl or methylpropargyl.

R 5 and R ¹⁵ as C 5 -C 12 cycloalkyl may be, for example, cyclopentyl, cyclohexyl, cyclooctyl or cyclododecyl.

R for aryl may be, for example, phenyl, tolyl or naphthyl.

R @ ¹⁵ and R @ ¹⁵ as an aralkyl group may be, for example, benzyl, phenylethyl or phenylpropyl.

When R @ ¹ and / or R @ ⁵ is A — CO--, this may, depending on the meaning of A, be a carboxylic acid residue such as acetyl, propionyl, butyryl, capronyl, capryloyl, lauroyl, acryloyl, crotonoyl, phenylacetyl, 3- (3,5-dl-trec, butyl-4-hydroxyphenyl) propionyl or benzoyl, or a carbamoyl residue such as methylcarbamoyl, butylcarbamoyl, dodecylcarbamoyl, diethylcarbamoyl, dihexylcarbamoyl, dioctylcarbamoyl or phenylcarbamoyl or a residue such as carbamoyl; for example ethoxycarbonyl, isopropoxycarbonyl, 2-ethylhexyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl or phenoxycarbonyl.

R ² may in accordance with its definition of Formula II are represented by the para- or meta-hydroxybenzyl. The substituents R ⁶ and R ⁷ present on the benzyl radical may be straight or branched (C 1 -C 9) alkyl groups such as methyl, ethyl, isopropyl, tert-butyl, n-hexyl, 1,1,3,3- tetramethylbutyl or t-nonyl. When R ⁶ or R ⁷ represents a cycloalkyl group, it may be, for example, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloalkyl. methylcyclohexyl. When R ³ or R ⁷ represents an aralkyl group, it may be, for example, benzyl or α, α-dimethylbenzyl. Preferably, R ⁶ and R ⁷ are C 1 -C 4 alkyl, especially methyl or tert-butyl.

According to the value of n may jednonebo ^R3 is a bivalent organic radical. For the C 1 -C 20 alkyl group, R ³ may be, for example, any of the above R ¹ alkyl radicals, but may further be a branched alkyl radical such as isopropyl, isopentyl, 2-ethylbutyl, 2- ethylhexyl or isononyl, or also higher alkyl radicals such as n-hexadecyl, n-octadecyl or n-eicosyl.

In the meaning of a substituted or interrupted alkyl group, R ³ may be, for example, any of the following: 2-phenoxyethyl,

2-benzyloxyethyl,

2-p-tolyloxypropyl, cyclohexylmethyl,

2,3-di (phenoxy) propyl,

2-phenylthioethyl,

2- (4-tert-butylphenylthio) ethyl,

2-acetylethyl,

2-isobutyrylethyl,

2- (dodecylcarbonyl) ethyl,

2-cyanoethyl, cyanomethyl,

3-cyanopropyl, methoxycarbonylmethyl, dodecyloxycarbonylmethyl,

2-ethoxycarboinylethyl,

1,2-di (methoxycarbonyl) ethyl,

2,3-di (ethoxycarbonyl) propyl,

2- (butylaminocarbonyl) ethyl,

2- (cyclohexyloxycarbonyl) ethyl,

2-tert-butyloxycarbonyl) ethyl,

2- (octadecyloxycarbonyl) propyl,

4- (proxycarbonyl) butyl,

2-acetoxyethyl,

1,2-diacetoxyethyl,

2- (isooctanoyloxy) propyl,

2- (octadecanoyloxy) ethyl

2- (cyclopentylcarbonyloxy) ethyl,

3-Benzoyloxypropyl

2- (p-tert-butylbenzoyloxy) ethyl,

2-salicyloyloxyethyl,

2- (3,5-di-tert-butyl-4-hydroxybenzoyloxy) ethyl,

2-phenylacetyloxyethyl,

2- (3,5-di-tert-butyl-4-hydroxyphenylpropionyloxy) propyl, dimethylphosphonomethyl,

2-Dimethylphosphonoethyl

2- (dioctylphosphono) ethyl, diphenylphosphonomethyl,

3- (diallylphosphonium) propyl, methoxymethyl,

2-butoxyethyl,

2-octadecyloxyethyl, isopropoxymethyl,

3-butylthiopropyl,

2-dodecylthioethyl,

2- (isohexylsulfinyl) ethyl,

2-octadecylsulfonylethyl,

2-ethyl-3-sulphonylpropyl,

2- (2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl) ethyl,

2- (1,2,2,6,6-Pentamethylpiperidin-4-ylaminocarbonyl) ethyl,

2- (2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl) -2- (methoxycarbonyl) hexyl; or

2,2-bis- (2,2,6,6-tetramethylpiperidin-4-ylaminocarbonyl) hexyl.

R 3 as an alkenyl or alkynyl group may be, for example, allyl, methallyl, 2-buten-1-yl, 3-hexen-1-yl, undecenyl, oleyl, propargyl or 2-heptin-1-yl.

Examples of R ³ as cycloalkyl, alkylcycloalkyl or cycloalkylalkyl groups are: cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclohexyl, propylcyclooctyl, hexylcyclododecyl, cyclomethyl, 3-cyclooctylpropyl or decahydronaphthyl or decahydronaphthyl.

Examples of R @ ³ as an aralkyl or alkylaralkyl group include benzyl, 2-phenylethyl, 2-phenylpropyl, β-naphthylmethyl, 4-methylbenzyl, 4-tert-butylbenzyl or 4-methylnaphthyl-1-methyl.

R ³ in the meaning of the group -O-CO-R ¹⁶ or -NH-CO-R ^ls may be for example acetoxy, propionoxy, butyroxyskupinu, oktanoyloxyskupinu, dodekanoyloxyskupinu, acryloxy krotonoxyskuplnu, benzyloxy, phenylacetoxy, 3,5-di-tert-butyl -4-hydroxybenzoyloxy, acetaminoskuipine, butyrylamino, decanoylamino, acryloylamino, benzoylamino or cyclohexylcarbonylamino.

When n is 2, then R ³ represents a direct bond or a divalent organic radical. The radical may be alkylene, such as methylene, ethylene or polymethylene of 20 carbon atoms, or the alkylene radical is interrupted by 1 or 2 hetero-members, such as divalent radicals:

—CH2O — CH2—, —CH2CH2O — CH2CH2—, —CH2CH2O — CH2CH2 — O — CH2CH2-, - (CH2) 3-S- (C1H2) 3-, —CH2CH2-S- (CH2) 4-S — CH2CH2- , —CH2CH2 — SO — CH2CH2—, —CH2CH2 — SO2 — CH2CH2—, —CH2CH2 — SO2— (CH2) 8 —SO2 — CH2C H2—, —CH2COOCH2CH200CH2-, —CH20H2COOCH2CH200CCH2CH2—, —CH2CH2 — COO (CH2) 4— OOC-CH 2 CH 2 -, -CH ₂ CH ₂ O ₆ (CH 2) 4 COOCH 2 CH _{2 -} , -CH ₂ CH ₂ OCO (CH 2) 8 COOCH ₂ CH 2 -.

Further, it may be an arene-bis-alkylene radical such as p-xylylene, benzene-1,3bis (ethylene), diphenyl-4,4‘-bis) methylene or naphthalene-1,4-bis (methylene). Finally, it may be a C 4 -C 8 alkenylene or alkynylene such as 2-buten-1,4-ylene, 2-butin-1,4-ylene or 2,4-hexadiin-1,6-ylene.

The compounds of formula I confer excellent protection on plastics against thermo-oxidative aging, such as light-induced aging. It is known that plastics can be stabilized by the addition of antioxidants or light-protective agents or mixtures of both, thereby greatly extending their shelf-life. On the other hand, stabilizers are also known which simultaneously have an anti-oxidant and a light-protective effect. Thus, 4-piperidinyl esters of mono- and di- (hydroxybenzyljmalonic acids) having a stronger stabilizing effect than the corresponding mixture of hydroxybenzyl malonate, known as an antioxidant and a derivative, have already been described in DOS 2,456,864.

4-piperidinol, known as a light protection agent. Now that the hydroxybenzyl or hydrogen atom in the compounds described in DOS No. 2,456,864 is replaced by an alkyl group or other group known to be inactive (as defined above for R ³ ), then surprisingly the antioxidant activity increases and efficiency, manifested by protection against the effects of light. The individual compounds of the formula I outperform all known stabilizers in certain plastics in terms of activity, which makes the invention of considerable importance for plastics technology.

Preferred are compounds of formula I wherein R ₃ to R _d are methyl and R ₍ , and R ₍ are hydrogen) or wherein R, and R ₍ are ethyl), R _b , R _d and R _o are methyl and R 3 _t is hydrogen. also preferred are compounds of formula I wherein X is oxygen or NH, ^R1 is hydrogen, -0 ', -OH, alkyl of 1-4 carbon atoms, allyl, propargyl, acetyl, acryloyl or crotonoyl,

R ² represents a hydroxybenzyl formula IIa or IIb,

R ⁷ R *

HO ^^ - CH _Z R ⁶

HO CH.

CH ₂ (Ub)

CH 2 in which

R ⁶ and R ⁷ are each independently C 1 -C 4 alkyl,

R ⁸ is hydrogen or methyl,

R ³ represents, when n = 1, an alkyl group having 1 to 18 carbon atoms, one or two groups -CN, -C (Oj-XR ¹² , -O-C (O) R ¹³ or -P (O) (OR ¹⁴ ) 2 substituted alkyl having 1 to 4 carbon atoms, wherein

R ¹² is C 1 -C 4 alkyl or C 1 -C 18 alkyl, carbon, C 5 -C 12 cycloalkyl, C 6 -C 18 alkylcycloalkyl, C 3 -C 6 alkenyl. C 1 -C 6 alkynyl, phenyl or C 7 -C 15 aralkyl or -OR ¹⁵ , wherein:

R ¹⁵ is C 1 -C 12 alkyl, allyl, propargyl or benzyl, or is -O-COR ¹⁶ or -NH-C ³ R ¹⁸ , wherein:

R ¹⁶ is C 1 -C 12 alkyl, phenyl, 3,5-di-tert-butyl-4-hydroxyphenyl or 2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl a group, or is a group of formula IIIb, or, if n is a number 2,

R ³ represents a direct bond, an alkylene group having 1 to 12 carbon atoms, one or two groups -O-, -S- or -CO-O-, an interrupted alkylene group. C 1 -C 12, furthermore denotes an arene-bis-alkylene group having 8 to 14 carbon atoms or an alkenylene group having up to 8 carbon atoms.

Particularly preferred are compounds of formula I wherein n is 1 or 2, R _a , R _b , R _c and R _d are methyl and R _e and R _f are hydrogen,

X is oxygen,

R ¹ is hydrogen, -O ', C 1 -C 4 alkyl, allyl or acetyl,

R ² represents a hydroxybenzyl formula IIa or IIb wherein ^R is t-butyl, R ⁷ is methyl or tert-butyl and R ⁸ is hydrogen or methyl and

R ³ represents a C 1 -C 18 alkyl radical which is substituted by 1 or 2 -C (Oj-OR ¹² ) groups, where R ¹² represents a C 1 -C 4 alkyl group or a group of formula IIIa

R ¹³ represents a C 1 -C 17 alkyl group, a cyclohexyl group, a phenyl group or a benzyl group; and

^R14 represents an alkyl group having 1 to 4 carbon atoms or an allyl group, followed by - O- or -S- interrupted alnebo is substituted by -P (O) (OR ¹⁴⁾ 2, wherein ^R14 is an alkyl group having from 1 to 4 carbon atoms, or R ³ is allyl, propargyl, benzyl, phenyl, alkylene having 1-8 carbon atoms or xylylene.

The present invention also encompasses salts of compounds of Formula I which are formed by addition of acids in maximum piperidine groups equivalent amounts. Such acids may be inorganic acids such as sulfuric acid, hydrochloric acid or phosphoric acid, organic carboxylic acids such as formic acid, acetic acid, oxalic acid, maleic acid, benzoic acid or salicylic acid, organic sulfonic acids such as methane or p-toluenesulfonic acid or phosphorus-containing organic acids such as diphenylphosphoric acid, methanephosphonic acid or diphenylphosphinic acid.

Examples of compounds of formula I are:

buityl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (2,2,6,6-tetramethyl-4-piperldinyl) ester, bis (1-allyl-2,2,6,6-tetramethyl) Allyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid -4-piperidinyl) bis, (1-hydroxyl-2,2,6,6-tetramethyl-4-piperidinyl) ethyl ester - (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid, propargyl- (3,5-di-tert-butyl) bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester 4-hydroxybenzyl) malonic acid, (3-methoxyethyl- (S-methyl-S.alpha.-dimethylbenzyl-4-hydroxybenzyl) malonic acid bis (2,2,6,6-tetramethy 1-4-piperidinyl) ester), dodecyl- (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) malonic acid bis (1-acrylic-2,2,6,6-tetramethyl-4-ipiperidinyl) ester, bis (1-acetyl-2) 2,6,6-tetramethyl-4-piperidinyl phenylthiomethyl- (3-tert-butyl-5-tert-amyl-4-hydroxybenzyl) malonic acid bis (1,2,2,6,6- dodecylthioethyl- (3-methyl-5-cyclohexyl-4-hydroxybenzyl) malonic acid pentamethyl-4-piperidinyl) ester bis (1,2,6,6-p) enitamethyl-4-piperidinyl ester dodecylsulfonylethyl- (3-methyl-5-cyclohexyl-4-hydroxybenzyl) malonic acid bis (1-oxide-2,2,6,6-tetramethyl-4-piperidinyl) methyloxycarbonyl ester methyl - (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (1-crotonyl-2,2,6,6-tetramethyl-4-piperidinyl) ester χ-octyloxypropyl- (3-methyl-5) di-tert-octyl-4-hydroxybenzyl) malonic acid bis- (1-formyl-2,2,6,6-tetramethyl-4-piperidinyl) -s-butylcarbonylethyl- (3,5-di-tert-butyl) ester 4-hydroxybenzyl) malonic acid bis (1-hydroxy-2,2,6,6-tetramethyl-4-piperidinyl) phenylsulfinylmethyl- (3,5-di-tert-butyl-4-hydroxybenzyl) ester malonic acid, β- (octyloxycarbonyl) ethyl- (3,5-di-tert-butyl-4-oxybenzyl) malonic acid bis (1-propyl-2,2,6,6-tetramethyl-5-piperidinyl) ester Acid, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester 1,2,2,6,6-pemtamethyl-4-piperidinoxycarbonylmethyl- (3,5-di-tert-butyl-4- hydroxybenzyl) malonic acid bis (2,2,2,6,6-tetramethyl-4-piperidinyl) benzyl- (3-methyl-5-di-tert-octyl-4-hydroxybenzyl) malonic acid ester, cyclohexyl- (2,3-dimethyl) (bis (2,2,6,6-tetramethyl 1-4-piperidinyl) ester) -5-tert-butyl-4-hydroxybenzyl) malonic acid bis (1,2,2,6,6-pentamethyl 1-4-piperidinyl) ester 2,2,6,6-tetramethyl-4-piperidinyl- I-Cyanoethyl- (3-isoproipyl-5-tert-butyl) (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester 4-hydroxybenzyl] malonic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) 3-diethylphosphonoethyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (bis (2,2,6,6-tetramethyl-4-piperidinyl) ester) bis ( 1-Benzyl-2,2,6,6-tetramethyl-4-piperidinyl Jester / 3-diphenylphosphonoethyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid, 1,4-di (3,5 - di-tert-butyl-4-hydroxyphenyl) -2,2,3,3-tetra (1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl) butane,

4,4'-di (3,5-di-tert-butyl-4-hydroxyphenyl) -3,3,3 ', 3'-tetra (2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl) dibutylsulfonate ,

4,4‘-di (3,5-di-tert-butyl-4-hydroxyphenyl) -3,3,3‘, 3‘-tetra (2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl) dibutyl ether,

3,3'-di (3,5-di-tert-butyl-4-hydroxyphenyl) -2,2,2 ', 2'-tetra (1-acetyl-2,2,6,6-tetramethyl-4) -piperidinylcarbonyl) -p-dipropylbenzene,

1,8-di (3,5-di-tert-butyl-4-hydroxyphenyl) -2,2 ', 7', 7 '-, tetra (1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl) oct-4-ene, ethylene di [α-3,5-di-tert-butyl-4-hydroxyphenyl-γ-bis (2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl) valerianate],

1,16-bis (3,5-di-tert-butyl-4-hydroxyphenyl) 197282

-2,2,15,15-tetrakis (1-oxyl-2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl) hexadecane, 1,8-bis (3-methyl-5-tert-butyl-4-hydroxyphenyl) enyl) -2,2,7,7-tetrakis (1-acetyl-2,2,6,6-tetramethyl-4-piperidinyloxycarbonyl) oct-4-in, bis (2, B-diethyl-2,5,6- butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid triniethyl-4-piperidinyl) bis (2,6-diethyl-2,5,6-itrimethyl-4-plperidinyl) ester allyl- ( Propargyl- (3,5-di-tert-3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (2,6-diethyl-1,2,5,6-tetramethyl-4-piperidinyl) ester butyl-4-liydroxybenzyl) malonic acid, dodecyl (2,6-dimethyl-4-tert-butyl-3) bis (1-acrylic-2,6-diethyl-2,5,6-trimethyl-4-piperidinyl) ester -hydroxybenzyl) malonic acid, dodecylsulfonylethyl- (3-methyl-5-cyclohexyl-4-hydroxybenzyl) malonic acid bis (2,6-diethyl-1,2,5,6-tetranomethyl-4-piperidinyl) ester, methyloxycarbonylmethyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (1-oxyl-2,6-diethyl-2,5,6-trimethyl-4-piperidinyl) ester, bis (1 Β- (octyloxycarbonyl) ethyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid, 2,6-tripropyl-2,6-dimethyl-5-ethyl-4-piiperidinyl ester, bis (2 Benzyl- (3-methyl-5-di-tert-octyl-4-hydroxybenzyl) malonic acid, 6-diethyl-2,5,6-trimethyl-4-piperidinyl) ester, bis (2,6-diethyl-1, 6-diethyl-2,5,6-trimethyl-4-piperidinyl) ester Cyclohexyl- (2,3-dimethyl-5-tert-butyl-4-hydroxybenzyl) malonic acid 2,5,6-tetramethyl-4-piperidinyl) ester bis (2,6-diethyl-1,2,5, 2,2,6,6-Tetramethyl-4-piperidinyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid 6-tetramethyl-4-piperidinyl) ester, bis (2,5,6,6) β-cyanoethyl- (3-isopropyl-5-tert-butyl-4-hydroxybenzyl) malonic acid tetramethyl-2-ethyl-4-piperidinyl) bis (2,6-diethyl-2,5,6-trimethyl-) 3-Diethylphosphonoethyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid 4-piperidinyl) ester,

1,4-di (3,5-di-tert-butyl-4-hydroxyphenyl) -2,2,3,3-tetra- (2,5,6-trimethyl-2,6-diethyl-4-piperidinyloxycarbonyl) ) butane.

The compounds of formula I can be prepared by various methods, which consist of different individual steps carried out in different order. The individual steps consist of reactions which are known, in particular those known from the chemistry of malonic acid derivatives.

The synthesis can be started by converting a lower alkyl ester of a malonic acid, such as diethyl malonate, by reaction with 4-piperidinol or 4-aminopiperidine V, respectively, to the corresponding bis-piperidinyl-malonic acid derivative VI:

CH 3 COOC 4 H 5 + ZHX

R @ ^{1 may} be the desired substituent present in the compound of formula (I) or piperidine derivatives which are not substituted on nitrogen may be used (V, R @ ¹ = HJ and R @ ¹ is introduced after the above reaction or later stages.

Introducing the proviso that both R ¹ may be carried out by conventional methods for N-alkylation or N-acylation, for example by reaction with alkylhalogenldy, alkenyl halides, propargyl chloride, benzyl chloride or carboxylic acid chlorides, preferably in the presence of a molar amount of a base. Hydroxyalkyl radicals are introduced by reaction with epoxides, for example ethylene oxide or propylene oxide, and can be converted to the corresponding N-acyloxyalkyl groups by reaction with carboxylic acid chlorides or anhydrides. When R ¹ is -O ', then the tall N-oxides can be produced from NH-compounds by oxidation with peracids or hydrogen peroxide. By reduction of such N-oxides, for example by catalytic hydrogenation, compounds with R ¹ = OH can be prepared.

As a next step can be added to compounds of formula VI either introduce first R ² and R ^3, or preferably first substltuemt R ³ and R ^2nd

The introduction of the hydroxybenzyl group R ² can be carried out by reaction with a hydroxybenzyldithiocarbamate of the formula

R ² -S-CS-N (R ²¹⁾ 2, wherein

R ²¹ represents an alkyl group having 1 to 5 carbon atoms, or both R ²¹ together with the nitrogen atom represent a morpholine, pyrrolidine or piperidine ring.

Such dithlocarbamates can be obtained by reacting phenol with formaldehyde, carbon disulfide and a secondary amine.

The reaction of the dithiocarbamates with the compounds of formula VI is carried out in a 1: 1 molar ratio in the presence of basic agents such as alkali metal hydroxides, alkali metal alkoxides, alkali metal or alkaline earth metal hydrides or alkali metal amides. These bases are preferably used in molar amounts, i.e. 1 equivalent of base is used per mole of dithiocarbamates. The reaction may be carried out in solution, for example in alcohols, ethers or hydrocarbons. Polar aprotic solvents such as dimethylformamide or dimethyl sulfoxide are also suitable. Preferably, the reaction is carried out in an alcoholic solution using an alkali metal hydroxide as the base.

Another suitable method for introducing hydroxybenzyl groups R ² in the compounds' of the formula VI is reacted with ^{i-hydroxybenzyl} amine of formula R ² -N (R ²¹ J2. Such amines can be prepared by reacting phenols with formaldehyde and a secondary amine so. Mannich reaction. The reaction was The compounds of formula (VI) are also accelerated with basic catalysts, preferably alkali metal amides or alkali metal alkoxides, but alkali metals are also suitable as catalysts, but unlike the process using dithiocarbamate, catalytic amounts of about 0.1 to 5 mol% of the basic catalyst are sufficient.

Instead of tertiary amines (Mannich bases), their quaternization products can also be used. Solvents of the above groups may be used as solvents, but may also be operated without a solvent.

When X is hydrogen, may be the radical R ² can also be introduced by a second synthesis of malonic acid ester by reacting an ester of formula VI is first converted by reaction with an equivalent of an alkali · metal, alkali metal alkoxide, alkali metal amide, alkali metal hydride or like alkali metal compound to the compound of formula VI with an alkali metal and then reacting the reaction product with 1 mole of a hydroxybenzyl halide of the formula R ² Hal (Hal = Cl, Br or J in a conventional manner) Although both of the above hydroxybenzylation methods are preferred, said method preferably used in those cases where it is heated accessible halogenated derivative R ² Hal.

Each of the three above methods leads to a derivative of an acid of formula VII hydroxybenzylmaionové to which must then establish R ^3rd

R-CH (COK - ^ -N- gfeytku R @ ³ / R \ _D ^Hc - (VII)

The introduction of the residue R ³ can be carried out either according to the classical method of C-alkylation of malonic acid esters by first converting the compound of formula VII to its alkali metal derivative and then reacting the derivative with a halogen derivative R ³ Hal or R ³ Hal ² . In this case, Hal is again chlorine, bromine or iodine. Depending on whether a compound of formula I in which n is 1 or 2 is required as a result of the synthesis, 1 mol of the monohalide of formula R ³ Hal or half a mole of the dihalogen derivative of formula R ³ Hal is used per mole of the alkali metal derivative of the compound VII. ₂ . Examples are alkyl, cycloalkyl, airalkyl, alkenyl or alkynyl halides and alkylene, alkenylene, alkynylene or xylylene dihalide. Further examples are haloicarboxylic acid esters, such as chloroacetic acid esters of mono- or dihydric hydroxy derivatives, or carboxylic acid halohydrin esters, such as 2-chloroethanol or 3-bromopropanol esters. Halophosphonic acid esters such as dimethyl chloromethyl phosphonate or diethyl 2-bromoethyl phosphonate are also suitable for this purpose.

derivative of iodine, then compounds of formula I are obtained in which n is 2 and R ³ is a direct bond.

Besides the classical methods of substitution on the carbon atom may be halogenated by means to introduce the radical R ³ using a method known. Michael addition, in which can be added a compound with activated dvoj197282 APPLICABLE bonds under the influence of basic catalysts to the central carbon atom of the compound of formula VII. The best known alternative is cyanoalkylation using acrylonitrile. However, acrylic and methacrylic esters, maleic esters, itaconic esters, vinyl ketones, vinyl sulfones, vinyl esters of carboxylic acids or vinyl phosphonic acid esters are also suitable. The catalysts used are used in an amount of from about 0.5 to 5 mole%. Examples of useful catalysts are alkali metal alkoxides, amides, hydrides or hydroxides or quaternary ammonium bases, such as benzyltrimethylammonium hydroxide, both in the classical substitution of malonic acid esters and in the Michael addition process, preferably in solution. Aprotic solvents, such as hydrocarbons or ethers, for example benzene, toluene, dioxane or tetrahydrofuran, or polar solvents, such as dimethylformamide, may be used.

Compounds of formula I in which R ³ is a radical of formula IV can be prepared by condensing two different malonic acid derivatives with formaldehyde in an approximately 1: 1: 1 molar ratio followed by the introduction of one or two hydroxybenzyl groups.

Compounds of formula I wherein R ³ is a group of formula III may be obtained by condensation of a malonic acid derivative of formula VI with 4-oxopiperidine followed by hydrogenation of the resulting piperidylidene derivative.

Special methods for introducing fosfonomethylových groups as substituents of R ³ involves reacting a malonic acid derivative of formula VII with formaldehyde and a phosphite of the formula P> ^(OR14) 3rd

Furthermore, a substituent R ³ can be introduced first according to one of the above methods, which can be converted to another R ⁵ group in a further reaction step. For example, a group can be introduced by addition of ethyl acrylate

R ³

-CH2CH2COOC2H5, which in the next step is converted to a divalent group by re-esterification with ethylene glycol

R ³ = - CH ² CH ² COOCH ² CH ² OOCCH ² CH 2 -.

In a similar manner, an intermediate haloalkyl group can be converted to a phenoxyalkyl or phosphonoalkyl group. Alkylthioalkyl groups can be converted by oxidation to the corresponding sulfoxides or sulfones. Such oxidation of the substituents R ³ may be carried out simultaneously with the introduction of oxygen as a substituent R ¹ , for example by oxidation with percarboxylic acids. It is also possible to introduce the radical R ¹ together with the radical R ³ if the radicals R ¹ and R ³ are identical, for example, as alkyl, alkenyl, propargyl or benzyl.

Based on these different options for carrying out the individual reaction steps, i.e. the introduction of the piperidinyl moiety, the introduction of the R ² group, the introduction of the R ³ 'group and optionally the introduction of the R ¹ residue, the order of the individual steps may be chosen as it seems most appropriate . In the examples below, it describes the introduction of the radical R ² as the last step. In principle, however, any other stage can also be selected as the last stage.

If the compounds of formula VI are first introduced with a substituent R ³ according to the methods described above, then intermediates of formula VIII are also obtained which are also novel

η (VIII) • P ³

The compounds of the formula I can be used according to the invention as stabilizers of plastics against their damage by oxygen, heat and light. Examples of such plastics are the polymers disclosed in DOS 2,456,864 on pages 12-14.

Of particular importance is the stabilization of polyolefins, styrene polymers and polyurethanes, for which malonates of formula I are particularly suitable. Examples of such plastics are, for example, higher and lower specific weight polyethylenes, polypropylene, ethylene-propylene copolymers, polystyrene, styrene, butadiene copolymers. acrylonitrile, mixtures of polyolefins or polymers of styrene, polyurethanes based on polyethers or polyesters in the form of lacquers, elastomers or foams.

The stabilizers are added to the plastics at a concentration of from 0.01 to 5% by weight, calculated on the stabilized material. Preferably, 0.03 to 1.5, particularly preferably 0.2 to 0.6% by weight of the compounds of formula (I) calculated on the stabilized material is incorporated into these polymers.

The incorporation of these stabilizers may be carried out after polymerization, for example by blending and optionally adding to the melt according to methods conventional in the art, before or during molding or by applying dissolved or dispersed compounds to the polymers, optionally with subsequent solvent evaporation.

The novel compounds can also be added to the stabilized plastics in the form of a parent rubber composition which contains these compounds, for example, in a concentration of from 2.5 to 25% by weight.

In the case of cross-linked polyethylene, the compounds are added prior to cross-linking.

In addition to the compounds of the formula I, other known stabilizers or co-stabilizers can be added to the plastics. Such can be, for example, antioxidants, light-protective agents or metal deactivators, or else co-stabilizers, such as, for example, phosphoric acid esters. In addition, other additives customary in plastics technology can be added, such as flame retardants, anti-static agents, plasticizers, lubricants, propellants, pigments, extenders or fillers.

The invention also relates to plastics stabilized with an additive of 0.01 to 5% by weight of the compound of the formula I, which may optionally contain still other known and customary additives. The plastics thus stabilized can be used in various forms, for example in the form of films, fibers, strips, profiles or as binders for lacquers, adhesives or sealants.

The present invention further provides compounds of formula VIII and their use as light protection agents for plastics. The substrates suitable for this purpose, the ratios in which they are used, and the methods of incorporation are the same as for the use of the compounds of formula I.

The preparation and use of the compounds of the invention are described in more detail in the following examples. Parts are parts by weight and percent by weight. Temperatures are given in degrees Celsius. Examples 1 to 31

23.3 g (0.05 mol) of butyl malonic acid bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) ester and 13.2 g (0.05 mol) of N- (3,5- di-tert-butyl-4-hydroxybenzyl) dimethylamine is dissolved in 200 ml of toluene. After the addition of 0.25 g of lithium amide, the mixture was heated under reflux for 4 hours. After cooling, the mixture is neutralized with 1.5 ml of a 1% acetic acid solution and the organic phase is washed several times with water. After drying over sodium sulfate, the solution was evaporated in vacuo. Butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) ester was obtained, m.p. 140 °.

The compounds described in Table I are prepared in an analogous manner:

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Butyl malonic acid bis (2,3,6-trimethyl-2,6-diethyl-4-piperidinyl) ester (26.2 g, 0.05 mol) and 13.2 g (0.05 mol) of N- (3.5 di-tert-butyl-4-hydroxybenzyl) dimethylamine is dissolved in 200 ml of toluene. After the addition of 0.25 g of lithium amide, the mixture was refluxed for 4 hours. After cooling, the reaction mixture was neutralized

1.5 ml of 1% acetic acid and the organic phase was washed several times with water. After drying over sodium sulfate, the solution was evaporated in vacuo. Butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (2,3,6-trimethyl-2,6-diethyl-4-piperidinyl) ester was obtained as a viscous oil No. 32).

Analysis for C 18 H 50 N 2 O 5:

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The compounds described in Table 1a are prepared in an analogous manner:

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13.2 g (0.03 mol) of ethyl malonic acid bis- (1,2,2,6,6-pentamethyl) ester and 9.75 g (0.03 mol) of N-diethyl-S- (3,5- of di-tert-butyl-4-hydroxybenzyl) dithiocarbamate is dissolved in 100 ml of isopropyl alcohol. While stirring, 1.2 g of sodium hydroxide (0.03 mol) in 12 ml of water are added dropwise at 60 DEG over 15 minutes. The reaction mixture was then heated at reflux for 2 hours, cooled to 50 °, 36 ml of 1% acetic acid was added and cooled to 0 °. The product crystallizes out and is recrystallized from ligroin. 12.7 g of ethyl (3,5-di-tert-butyl-α-hydroxybenzyl) -matic acid bis (1,2,2,6,6-pentameithyl-4-hydroxybenzyl) ester, m.p. 166 °, are obtained.

The compounds listed in Tables IIa and IIb are prepared in an analogous manner using the corresponding dlthiocarbamates.

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Examples 43—46

Κ 24.6 g (0.06 mol) of ethyl malonic acid fls (2,2,6,6-tetramethyl-4-pipericyl) ester in 80 ml of dimethylformamide are added

2.5 g of sodium hydride dispersion (55 to 60 percent), then 13.6 g (0.06 mol) of 2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl chloride in 40 ml of dimethylformamide. After stirring at 90-100 ° for 23 hours, the reaction mixture was poured into ice water, the aqueous solution was extracted with ether, dried over sodium sulfate and the solvent was evaporated in vacuo to give bis (2,2,6,6-tetramethyl). Ethyl (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) malonic acid -4-piperidinyl ester as an oily yellowish residue (Compound No. 43).

The following compounds were prepared in an analogous manner: Compound No. 44:

Ethyl (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) malonic acid bis (1,1,2,2,6,6-pentamethyl-4-piperidinyl) ester, m.p. 45:

butyl (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) malonic acid bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, yellow oil, Compound No. 46:

butyl- (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) malonic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester, oil.

Example 1 a d 47

21.9 g (0.05 mol) of bls (1,2,2,6,6-pentamethyl-4-piperidinyl) ethyl malonic acid ester, 20.5 g (0.05 mol) bis (1,2,2,6) Malonic acid 6-peintamethyl-4-piperidinyl ester, 1.5 g (0.05 mol) paraformaldehyde and 0.5 g sodium hydride are stirred in 120 ml toluene for 0.5 hours at room temperature and then for 7 hours at boiling point After cooling, 13.2 g (0.05 mol) of N- (3,5-di-tert-butyl-4-hydroxybenzyl) dimethylamine are added and the mixture is heated under reflux for 4 hours. Working up analogously to Example 1 gives 1- (3,5-di-tert-butyl-4-hydroxyphenyl) -2,2,4,4- (1,2,2,6,6-pentamethyl-4- Piperidinyloxycarbonyl) hexane as an oily residue.

Analysis:

calculated:

71.2 o / o C, 10.3 θ / o H, 5.2% N, found:

70.3 o / c, 10.5% H, 5.3% N. Examples 48-49 g of butyl (3,5-) - (2,3,6-trimethyl-2,6-diethyl-4-piperidinyl) ester. di-tert-butyl-4-hydroxybenzyl) malonic acid (Compound No. 32) was dissolved in 200 mL of xylene. 20 g of anhydrous potassium carbonate and 10 g of acetic anhydride are then added at room temperature and the suspension is slowly warmed until a rapid evolution of carbon dioxide occurs. Once the evolution of carbon dioxide is complete, the temperature is further raised to 139-135 ° and the mixture is stirred at reflux for 10 hours. After cooling, the potassium salts were filtered off and the xylene solution was evaporated in vacuo. Butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis (1-acetyl-2,3,6-dimethyl-2,6-diethyl-4-piperidinyl) ester remains acid.

Analysis:

calculated:

% C, 72.77;% H, 10.26;% N, 3.39.

% C, 72.80;% H, 10.10;% N, 3.50.

Analogously, 32 g of bis- (2,2,6,6-tetramethyl-4-piperidinyl) butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid are reacted with 10 g of acetic anhydride and 20 g of potassium carbonate to give butyl- (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid bis- (1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl) ester which melts at 120-124 °.

Examples 50-53

(Compound 50, R ³ = C ⁴ H 9) g N, N'-di- (2,2,6,6-tetramethyl-4-piperidinyl) di-butyl malonic acid (0.1 mol) and 26.4 g N- (3.5 di-tert-butyl-4-hydroxybenzyl] dimethylamine (0.1 mol) was heated in 450 ml of toluene for 4 hours with the addition of 0.5 g of lithium amide to reflux and after cooling the mixture was neutralized with 0.4 g of glacial acetic acid. The residue was purified to give crude N, N'-di- (2,2,6,6-tetramethyl-4-plperidinyl) diamide butyl- (3,5-di-tert-butyl-4-) as a residue. hydroxybenzyl) malonic acid, which melts at 244 ° after recrystallization from ethanol.

Compounds 51, R ³ = C ² H 5, and 52, R ³ = n-CeH 17 were prepared analogously.

51:

Ethyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid N, N‘-di- (2,2,6,6-tetra-methylpiperidin-4-yl) diamide, m.p. 240-241 °,

52:

N, N ^i-di- (2,2,6,6-tetramethylpiperidin-4-yl-N jdiamid oíctyl- (3,5-tert-butyl-4-hydTOxybenzyljmalonové acid, mp 182-184 °.

53:

Benzyl- (3,5-di-tert-butyl-4-hydro-xyl) -benzyl-malonic acid N, N‘-di- (2,2,6,6-tetramethyl) -piperidin-4-yl) -amide, m.p.

104-114 °.

Examples 54—60

The following compounds 54-60 were prepared in an analogous manner to that described in Example 1.

Merge no.

Melting point ° C

OH n-C 6 H 13 benzyl benzyl benzyl

CH3

CH 3 - C 4 H 9 - C 4 H 9 ch ₃

- benzyl CH ₃ ^CH i

-C4H9 —C12H25

114-118 ° oil

120-125 °

170 °

145 °

181 ° oil

Example 61

By the method described in Example 48, butyl- (3,5-di-tert-butyl-4) bis- (1-acryloyl-2,2,6,6-tetramethyl-4-piperidinyl) ester was prepared by reacting Compound No. 2 with acryloyl chloride. -hydroxybenzylmalonic acid, which melts at 120 to 124 °.

Examples 62 and 63

Compounds 62 and 63 were prepared analogously to Example 1.

CH ₃ CH ₃ (CH ₃ -NH ² -COO) _from CR ³ -C (COO C 1 CH ₃ CH ₃ CH ₃ CH ₃

(CU J

OH

ClCH 3 compound 62, compound 63,

R ³ = - (CH 2) 8 -, R ³ =

-cwkoy-c ^.

mp 168-170 ° mp 130 °.

Example 64

Thermal stabilization of polypropylene

Stabilizer number .Number of days to starting decomposition 149 ° 135 °

100 parts of polypropylene (melt index 3.2 g / 10 min, 230 ° / 2160 gj) are vigorously mixed in a shaking apparatus with 0.2 parts of the stabilizer listed in the following table for 10 minutes. The resulting mixture is kneaded in a Brabender plastograph at a temperature of 200 DEG C. for 10 minutes, and the mass thus obtained is then compressed into 1 mm thick sheets on a plate press at 260 DEG C. The strips of 1 cm width and 17 cm length are punched from the stamped films.

Testing of the efficacy of the additives added to the test strips is carried out by hot aging in an air circulation oven at 135 ° and 149 °, the strips without additive being used for comparison. For this purpose, 3 strips are used from each composition. The finite state is defined as the state where the weakly visible pulverization of the test strip occurs.

TABLE III

Stabilizer Number of days number up to starting decomposition

149 ° 135 °

none 1 3 1 27 Mar: 84 2 9 55 3 20 May 51 4 25 66 5 9 53 6 21 68 8 23 65 10 15 Dec 57 11 26 77 13 49 141 14 45 104 15 Dec 45 103 16 29 96 18 37 126

21 11 50 23 7 32 24 27 Mar: 75 25 14 66 26 5 33 27 Mar: 8 32 29 20 May 20 May 30 30 77 31 23 67 33 14 53 34 16 57 35 4 26 36 25 66 37 8 45 38 8 43 39 20 May 58 40 20 May 51 42 16 61 44 29 79 45 28 77 46 24 73 47 5 13 48 14 53 50 12 38 51 9 34 52 16 43 53 12 46 54 4 12 56 17 85 57 17 17 58 9 40 59 24 74 60 15 Dec 54 61 9 50 62 26 82 Example 65

Thermal stability of polypropylene:

In addition, several of the samples described in Example 64 were tested for their color fastness, namely:

(a) after processing (Table IV, column 2), bj after 500 hours of exposure at the Hanau. xenotest (Table IV, column 3),

(c) after a one-week treatment with boiling water (Table IV, column 4).

An empirical color scale was used to assess the color in which the number 5 is colorless, 4 is also an acceptable weak color, while the numbers 3, 2 and 1 are increasing in color.

Stabilizer, example number

8

Ů8 21

27 Mar:

62

TABLE IV

Assessment of color according to scale 1 to 5 after treatment after treatment after exposure to boiling water 1 week - 5 4 - 5 4 - 5 4 - 5 - 4 4-5 - 5 4 - 5 4 - 5 4 - 5 4-5 4 - 5 4 - 5 4-5 - 4 4-5 - 5 4 - 5 4 - 5 4 - 5 4 - 5 4 - 5 - 4 - 5 4 - 5 4 - 5 4 - 5 4 - 5 4 - 5 4 - 5 - 4 - 5 - 5 4-5

5 5 - 5 4 - 5 4 - 5 - 5 - 5 - 5 - 4 - 5 - 5 4 - 5 4 - 5 4 - 5 4 - 5 4-5 4 - 5 - 3 4 - 5 - 5, 4 - 5 4 - 4 - 5 4 - 5 4 - 5 4 - 5 ^; 4 - 5 4 - 5 4 - 5 - 5 4 - 5 4 - 5 - 5 - 5 4 - 5 4 - 5

Example 66

Protect polypropylene from light

100 parts of polypropylene powder (Μορlem, Fiber grade, Montedison) are homogenized with 0.2 parts of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid octadecyl ester and 0.25 parts of the stabilizer listed in the following table 5 in a Brabender plastograph at 200 ° for 10 minutes. The mass obtained in this way is removed as quickly as possible from the kneading machine, and in a lever press 2 to 3 mm thick plates are pressed from the mass. A portion of the obtained crude compacts was cut and pressed between two highly polished hard aluminum sheets using a manual hydraulic laboratory press for 6 minutes at 260 ° and 12 t pressure to 0.5 mm thick sheets, which were immediately cooled rapidly in cold water. A test film of 0.1 mm thickness is produced from this film of 0.5 mm thickness under exactly the same conditions. 60 x 44 mm samples are now cut from this foil using punches and illuminated in a xenotest device. At regular time intervals, these samples are removed from the illuminator and examined by means of an IR spectrophotometer for carbonyl groups. The increase in carbonyl extinction at 5.85 ₍ .mu.m in illumination is a measure of photooxidative degradation of the polymer [see L. Balaban et al., J. Polymer Sci. Part C, 22, 1959-1071 (1969), JF Heacock, J. Polymer Sci. Part Al, 22, 2921-34 (1969), DJ Carlson and DM Wiles, Macromolecules 2, 587-606 1969)] and has been reported to be associated with a decrease in the mechanical properties of the polymer. Thus, for example, the film is completely brittle when reaching a carbonyl extinction of about 0.300.

The protective effect of the stabilizers according to the invention is shown in Table V below:

TABLE V Stabilizer, Exposure Time in hours to Example No. to achieve CO-extinction = 0.3

Stabilizer, Exposure time in hours to --- ^; -

example no. to achieve CO-extinction = 0.3 38 39 6 400 7 080 Comparative substance 800 44 5 500 1 11700. 45 5 800 3 6 500 46 7 300 4 5 800 47 7 600 5 3 700 • 50 5 850 6 3 700 51 5 000 8 7 600 52 5 150 10 6 080 53 2 900 11 4 580 54 5 200 13 5 800 56 4 000 14 6 200 57 3 970 15 Dec 6 803 58 3 970 16 4 000 59 6 800 18 5 200 61 5 560 12 8 990 62 5 040 22nd 5 790 24 5 160 Example 67 25 6 680 26 5 600 Comparison of protection against light 27 Mar: 9 000 with the state of the art: 28 6 200 29 5 750 For comparison with protective effect 30 3 460 valuables known from DOS 2,456,864 to light 31 7 300 the compounds listed in 33 3 200 following the table method described in 34 6 900 I put 66 on the effect of protecting polypropylene 35 6 500 light film. Sample preparation is also 36 6 900 described in Example 66. 37 7 000

Rl

R ⁴

CH 3 -C (CH 3) 3

CH 3 -C (CH 3) 3

H — C (CH3) 3

H -C (CH 3) s

H —CH3

H -CH 3

TABLE VI> 2

Rí /? '

R-Nry-OOC-C-CH3-O-ow

^CW 3 CHj

CÍCHjjj

R ^{1 2}

Compound of

The exposure time to achieve the absorbance of 0,3--C4H9 .CfOCP _{3; 3}

j-UP _{3 3} -C4H9 /

~ ^C ^ 7 \ Cy OP Example 1

DOS 2 456 864 Example 2

DOS 2,456,864 Example 3

DOS 2,456,864

730 hours

030 hours

660 hours

070 hours

500 hours

680 hours

Example 68

Protection of acrylonitrile-butadiene-styrene copolymer from light effects

100 parts of acrylonitrile-butadiene-styrene copolymer, polymerized in 13% butadiene and 65% styrene, are mixed with 0.2 parts of 3,5-di-tert-butyl-4-hydroxytoluene and 0.3 parts of tris-nonylphenyl phosphate and 1 part. the light-retardant listed in Table VII below on a calender for 4 minutes, one cylinder rotating at 18 rpm and heated to 170 ° C. The second roller is rotated at a slower speed (16 rpm) and heated to 160 [deg.] C. Then 2 mm thick plates are pressed from this mixture for 2 minutes at 175 [deg.] These plates are measured in a xenotest 450 apparatus. The light exposure is determined by the infrared spectrum of the carbonyl group, which is determined by means of a photometer. Table VII shows the exposure time at which the CO extinction ratio to 1450 · cm ^-1 increases to 0.1. This CO extinction corresponds to a reproducible decrease in the impact toughness of the samples.

TABLE VII <s>

Compound number

Time needed until

Eco at 1720 cm ^-1 Ech ₂ at 1450 cm ^-1

0.1 without stabilizer

900 hours

1100 hours

300 hoidln

Example 69

Protection of polyurethane foils against the effects of light

100 parts of the aromatic polyester polyurethane (Estane ^R 5707, from Goodrich) are cold dissolved in 400 parts of dimethylformamide. To this solution was added 0.5 parts each of the stabilizer listed in Table VIII below. Using a film-forming device adjusted to a thickness of 500 µm, a film is formed on the glass plate and dried in an air circulation oven at 120 ° for 20 minutes. Films having a thickness of about 60 .mu.m are obtained. The samples are illuminated in a xenotest 1200 device. The length of time for which the loss of transrnise (or corresponding absorption) of light of 420 nm wavelength is 15% is determined. This loss of transmission is a measure of the yellowing produced. Further, in the elongation test, the length of the elongation is 50 percent of its original value.

Stabilizer

TABLE VIII

Time to stretch to 50%

Time at which transmission loss of .15% without stabilizer is 0.5% of Compound No. 1 0.5% of Compound No. 2 0.5% of Compound No. 6 hours

650 hours 440 hours 280 hours

100 hours: 950 hours> 1000 hours 280 hours

Claims (3)

What is claimed is: 1. A method for stabilizing plastics against damage caused by oxygen, heat and light, characterized in that 0.01 to 1 is added to the plastics material. 5% by weight of a compound of formula I wherein n is 1 or 2, R _a represents an alkyl group having 1 to 6 carbon atoms, R _b represents an alkyl group having 1 to 6 carbon atoms, R _c represents a C 1 -C 9 alkyl group, a phenyl group, a benzyl group or a phenylethyl group, R _d represents an alkyl group having 1 to 6 carbon atoms; or R _c and R _d together are tetramethylene or pentamethylene, R _e is hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl, or (C 8 -C 8) aralkyl; R _f is hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl, (C 7 -C 8) aralkyl, and X is oxygen or -NR-, even where R is hydrogen, C 1 -C 18 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 5 -C 12 cycloalkyl , (C 6 -C 19) aryl or (C 7 -C 9) aralkyl, R ¹ denotes hydrogen, -O ', -OH, C 1 -C 12 alkyl, C 3 -C 4 alkenyl, propargyl, benzyl or -CH 2 -CH (OR ⁵ ) -R ⁴ , where R ⁴ is hydrogen, methyl or phenyl; and R ⁵ is hydrogen or A-CO-, or the radical R ¹ is represented by A - CO--, and in both cases, A is C 1 -C 12 alkyl, C 2 or C 3 alkenyl, cyclohexyl, phenyl, benzyl, furthermore phenyl or phenylethyl which is substituted with 2 C 1 -C 4 alkyl groups and hydroxyl, furthermore C 1 -C 12 alkylamino, C 2 -C 16 dialkylamino, anilino, C 1 -C 12 alkoxy, henzyloxy or phenoxy. R ² represents a hydroxybenzyl group of formula II wherein R ⁶ and R ⁷ are each independently C 1 -C 9 alkyl, C 7 -C 9 aralkyl or C 5 -C 8 cycloalkyl, and R ⁸ is hydrogen or methyl, and R ³ is alkyl when n = 1. C 1 -C 20 or one or two groups -OR ⁹ , -SR ¹⁰ , -CO-R ¹¹ ,-CN, -C (O) YR ¹² , -O-C (O) R ¹³ , -P ( O) (OR ¹⁴ ) 2 substituted alkyl having 1 to 10 carbon atoms, wherein R ⁹ represents a phenyl or C 6 -C 10 alkylphenyl, benzyl or cyclohexyl group, R ¹⁰ represents a phenyl group or an alkylphenyl group of 6 to 10 carbon atoms, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, Y is oxygen or -NR- and R is as defined above, R ¹² represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a group of formula III in which: R ¹⁷ has the meaning given for R ¹ , and R _a , R _b , R _c , R _d , R _c , R _f are as defined in formula I, R ¹³ represents an alkyl group having 1 to 17 carbon atoms, cycloalkyl having 5 to 12 carbon atoms or phenyl or phenylalkyl of 7 to 9 carbon atoms, wherein the phenyl radical is optionally substituted by alkyl having 1 to 4 carbon atoms and / or hydroxyl group, R ¹⁴ is C 1 -C 8 alkyl, allyl or phenyl and X is as defined above, R @ ³ is furthermore a —S--, —S--, —SO— or —SO2 - interrupted alkyl group having 2 to 22 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, a cycloalkyl group (C 5 -C 12) alkyl, (C 6 -C 18) alkylcycloalkyl, (C 6 -C 14) cycloalkylalkyl, aralkyl or C 7 -C 19 alkylalkyl, phenyl or -OR ¹⁵ group, wherein: R ¹⁵ is C 1 -C 18 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl (C 4 -C 12) cycloalkyl, (C 5 -C 12) cycloalkyl or (C 7 -C 9) aralkyl or R ³ is furthermore -O-C (O) R ¹⁶ or -NH-C (O) R ¹⁶ , whereas R ¹⁶ represents a C 1 -C 12 alkyl group, a C 2 -C 3 alkenyl group, a cyclohexyl group, a phenyl group, a benzyl group, two C 1 -C 4 alkyl groups and a phenyl or phenylethyl substituted hydroxyl group; or the symbol R ³ represents a group of formula III or group IV R18 CO — Y — R ¹⁹ / —CH2— c \ CO-Y-R ²⁰ (IV) wherein R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms, allyl, benzyl, phenyl, cyclohexyl, alikoxyalkylovou group having 3-8 carbon atoms or one of the above defined groups -O-C (O) R ¹⁶ or -NH - <C (O) R ¹⁶ , or having any of the meanings given for R ² , and r ¹⁹ _and p 20 are, independently of one another, C 1 -C 6 alkyl or the radical of formula III, or if n is 2, Then symbol R ³ represents a direct bond, an alkylene group having 1 to 20 carbon atoms, further one or two groups "O", "S", "SO", "SO 2" or a "CO-O" interrupted alkylene group having 2 to 20 carbon atoms , an arylene-bis-alkylene group having 8 to 14 carbon atoms, an alkenylene group having 4 to 8 carbon atoms or an alkynylene group having 4 to 8 carbon atoms, or an acid addition salt thereof. 2. A method according to claim 1, characterized in that from 0.01 to 0.1 is added to the plastic 5% by weight of a compound of formula (Ia) wherein m is 1 or 2, R _a represents an alkyl group having 1 to 6 carbon atoms, R _b represents an alkyl group having 1 to 6 carbon atoms, R _c represents a C 1 -C 9 alkyl group, a phenyl group, a benzyl group or a phenylethyl group, R _d represents an alkyl group having 1 to 6 carbon atoms, or R _c and R _d together are tetramethylene or pentamethylene, R _e represents hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl or (C 7 -C 8) aralkyl group, R _f is hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl, (C 7 -C 8) aralkyl, and R ¹ is hydrogen, -O ^-, -OH, alkyl of 1 to 12 carbon atoms, alkenyl having 3 or 4 carbon atoms, propargyl, benzyl or a group of formula -CH CH (OR ⁵ j - R ^4, where R ⁴ is hydrogen, methyl or phenyl; and R ⁵ is hydrogen or A-CO-, or R ¹ is A-CO, and in both cases A is C 1 -C 12 alkyl, C 2 or C 3 alkenyl, a cyclohexyl group, a phenyl group, a benzyl group, furthermore a phenyl or phenylethyl group which is substituted by 2 alkyl groups of 1 to 4 carbon atoms each and a hydroxyl group, furthermore an alkylamino group of 1 to 12 carbon atoms, a dialkylamino group of 2 to 16 carbon atoms , anilino, C 1 -C 12 alkoxy, benzyloxy or phenoxy groups, R ² represents a hydroxybenzyl group of the formula II _R TR HIM CH, (ID in which R ⁶ and R ⁷ independently represent C 1 -C 9 alkyl, C 7 -C 9 aralkyl or C 5 -C 8 cycloalkyl, and R ⁸ is hydrogen or methyl, and R ³ , when n = 1, is an alkyl group having 1 to 20 carbon atoms or one or two groups -OR ⁹ ,. -SR ^10, -CO-R ^11, -CN, ^-CO-OR12, -O-C (O) R ^13, -P (O) ^(OR14) 2, alkyl having 1 to 10 carbon atoimy wherein R ⁹ represents a phenyl or C 6 -C 10 alkylphenyl, benzyl or cyclohexyl group, R ¹⁰ represents a phenyl group or an alkylphenyl group of 6 to 10 carbon atoms, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, R ¹² is C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl Illb carbon atoms or ^R * -R ¹ R _c (Illb) R _b , R _c , Rd, R _e , R f have the aforementioned R ¹ , R _and n are significant R ¹³ represents a C 1 -C 17 alkyl group, a C 5 -C 12 cycloalkyl group or a phenyl group or a C 7 -C 9 phenylalkyl group, the phenyl radical being optionally substituted by a C 1 -C 4 alkyl group and / or hydroxyl group, R ¹⁴ is C 1 -C 8 alkyl, allyl or phenyl, and R &lt; ³ & gt ^; is furthermore an -O-, -S-, -SO2- or -SO2- interrupted alkyl group having 2 to 22 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, a cycloalkyl group (C až-C uhlíku) alkyl, (Cc-C alkyl) alkylcycloalkyl, (C až-C 14) cycloalkylalkyl, (C až-C 19) aralkyl or (C až-C alky alky) alkyl group or, if n is 2, the symbol R ³ represents a direct bond, alikylenovou group having 1 to 20 carbon atoms, also one or two groups -0-, - S-, -SO-, -SO 2 or -CO-O-, alikylenovtou interrupted group with 2-20 carbon or a C 4 -C 8 arylene-bis-alkylene group, a C 4 -C 8 alkenylene group or a C 4 -C 8 alkynylene group, or an acid addition salt thereof. 3. Process according to claim 1 or 2, characterized in that the plastic material is added from 0.01 to 5 wt% of a compound of formula VIII R ³ "(VTN) wherein n is 1 or 2; R represents alkyl _and (C 1 -C 6) group R _b is C 1 -C 6 alkyl, ¹ R _c is C 1 -C 9 alkyl, phenyl, benzyl or phenylethyl, R _d represents an alkyl group having 1 to 6 carbon atoms, or R _c and R _d together represent a tetramethylene group or a pentamethylene group, R _c is hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl or (C 7 -C 8) aralkyl group, R f is hydrogen, (C 1 -C 5) alkyl, (C 3 -C 4) alkenyl or (C 4 -C 4) alkynyl, or C 7 -C 8 aralkyl, and X represents oxygen or the group -NR-, where R is hydrogen, (C 1 -C 18) alkyl, (C 3 -C 4) alkenyl, (C 3 -C 4) alkynyl, (C 5 -C 12) cycloalkyl, (C 6 -C 10) aryl, or- (C7 -C9) aralkyl group; R ¹ is hydrogen, -O ', -OH, C 1 -C 12 alkyl, C 3 -C 4 alkenyl, propargyl, benzyl, or -CH 2 -CH (OR ⁵ ) -R ⁴ , where R ⁴ is hydrogen, methyl or phenyl; and R ⁵ is hydrogen or A-CO-, or R ¹ is A-CO-, and in both cases A is C 1 -C 12 alkyl, C 2 or C 3 alkenyl, cyclohexyl , phenyl, benzyl, furthermore is phenyl or phenylethyl which is substituted by 2-alkyl groups having from 1 to 4 carbon atoms each and hydroxyl group, furthermore represents alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 2 to 16 carbon atoms , anilino, C 1 -C 12 alkoxy, benzyloxy or phenoxy groups, R ³ , when n = 1, is an alkyl group having 1 to 20 carbon atoms or one or more groups -OR ⁹ , -SR ¹⁰ , -CO-R ¹¹ , -CN-, -C (O) YR ¹² , —O — C (O) R ¹³ , -P (O) (OR ¹⁴ ) 2, substituted C 1 -C 10 alkyl, wherein R ⁹ represents a phenyl or C 6 -C 10 alkylphenyl, benzyl or cyclohexyl group, R ¹⁰ represents a phenyl group or an alkylphenyl group of 6 to 10 carbon atoms, R ¹¹ represents an alkyl group having 1 to 12 carbon atoms, Y is oxygen or -NR- and R is as defined above, R ¹² represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a group of formula III '-R * R _c (III) wherein R ¹ , R _a , R _b , R c, Rd, R e, R t are as defined above, R ¹³ represents a C 1 -C 17 alkyl group, a C 5 -C 12 cycloalkyl group or a phenyl group, optionally a C 7 -C 9 phenylalkyl group, the phenyl moiety being optionally substituted by a C 1 -C 4 alkyl group and / or hydroxyl group, R ¹⁴ is C 1 -C 8 alkyl, allyl or phenyl and X is as defined above, R ³ is furthermore a —Ο—, —S—, —SO— or —SO2 — interrupted alkyl group having 2 to 22 carbon atoms, an alkenyl group having 3 to 18 carbon atoms, an alkynyl group having 3 to 8 carbon atoms, a cycloalkyl group with 5-12 carbon atoms, alkylcycloalkyl group having 6 to 18 carbon atoms, a cycloalkylalkyl group with 6 to 14 carbon atoms, an aralkyl group or alfcylaralkylovou group having 7-19 carbon atoms, phenyl Neibu -OR ^15, wherein R ¹⁵ is C 1 -C 18 alkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 5 -C 12 alkyl or C 7 -C 9 aralkyl, or R ³ is furthermore a group -O-C (O) R ¹⁶ or a group -NH-C (O) R ¹⁶ , wherein R ¹⁶ is C 1 -C 12 alkyl, C 2 -C 12 alkenyl, cyclohexyl, phenyl, benzyl, two C 1 -C 4 alkyl and phenyl or phenylethyl substituted hydroxyl, or the symbol R ³ represents a group of formula III or group IV Rl » CO — Y — R ¹⁹ Z —CH 2 —C \ CO-Y-R ²⁰ (IV) wherein R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms, an allyl group, a benzyl group, a phenyl group, a cyclohexyl group, a C 3 -C 8 alkoxyalkyl group or one of the above-defined groups -O-C (O) R ¹⁶ or -NH -C (O) ^R16 or has one of the meanings given for ^R2 and R19 _and R20 are independently alkyl groups having 1 to 6 carbon atoms or a radical of formula III or, if n is 2, then the symbol R ³ is a direct bond, an alkylene group having 1 to 20 carbon atoms, also one or two groups -0-, -S-, -SO-, -SO 2 -, -CO-O- or interrupted by an alkylene group having 2 to 20 carbon a C 4 -C 14 arylene-bis-alkylene group, a C 4 -C 8 alkenylene group or a C 4 -C 8 alkynylene group, or an acid addition salt thereof.