FR2718743A1 - Bisphenyl phosphites of hindered amine light stabilizing compounds monomers and oligomers useful as stabilizers. - Google Patents

Abstract

New monomeric compounds of formula I and new oligomeric compounds of formula II (CF DRAWING IN BOPI) in which the generic symbols have the definition given in claim 1 are described as stabilizers of organic materials against degradation due to oxidation , heat or light.

Description

The present invention relates to novel bisphenylphosphites of HALS

  (Hindered Amine Light Stabilizer) monomers and oligomers, compositions containing an organic material, preferably a polymer, and novel monomeric and oligomeric HALS bisphenylphosphites, and their application for the stabilization of materials

  oxidation, heat or light degradation.

  Organic phosphites are known in the art as costabilizers, secondary antioxidants and shaping stabilizers, inter alia for polyolefins; examples of such known phosphite stabilizers are found in R. Gichter / H. Muller (Ed.), Plastics Additives Handbook, 3rd edition,

  p. 47, Hanser, Munich, 1990, and in EP-A-356,688.

  Hindered amines, in particular compounds containing 2,2,6,6-tetramethylpiperidyl groups, are preferably used.

  as light stabilizers (Hindered Amine Light Stabilizers; HAIS).

  Phosphites having HALS-type structural elements are described for example by T. Konig et al., J. Prakt. Chem. 334, 333-349 (1992) and in

  patent documents US-A-5,239,076, GB-A-2,247,241, DE-A-4,306,747 and FR-A-

A-2,380,290.

  There is also a need for active stabilizers for materials

  Organic compounds susceptible to degradation due to oxidation, heat and / or light.

  It has now been found that a selected group of such HALS phosphites is particularly suitable for the stabilization of organic materials sensitive to degradation under the effect of oxidation, heat or light. In particular, the value of the compounds mentioned as stabilizers for

  In form for synthetic polymers.

  The present invention thus relates to monomeric compounds of formula I and oligomeric compounds of formula II

H3C CH3 R R H3C CH3

RF N X-P-O 0-P X N-R 4

H3C CH3 A -, 3H

R3 R3

R1 P.,

(i) R4

H3CICH3

R1 R X

A RP

  wherein R1 and R2 independently of one another are hydrogen, C1-C25 alkyl, C2-C24 alkenyl, C5-C8 cycloalkyl unsubstituted or substituted by C1-C4 alkyl; phenyl which is unsubstituted or substituted by C1-C4 alkyl; C5-C8 cycloalkenyl unsubstituted or substituted with C1-C4 alkyl; or C 7 -C 9 phenylalkyl, R 3 represents a hydrogen atom or a methyl residue, R 4 represents a hydrogen atom or a C 1 -C 8 alkyl residue, O, OH, NO, -CH 2 CN, C 1 -C 8 alkoxy, Cal-C-cycloalkoxy, C3-C6 alkenyl, C3-C6 alkynyl, C₁-C8 acyl, C phén-C9 phenylalkyl unsubstituted or substituted on the phenyl ring by C₁-C alkyle alkyl; R 5 A represents an oxygen or sulfur atom or the residue C--, I Rs I8 II II II

  -CH2C Y CC2CH2COYOCC2CH2- or (CH2) -O-C-Z-C-O- (CH2);

  X represents an oxygen atom or / -R7, Y and Z represent, independently of one another, a C2-C18alkylene or C4-C18alkylene radical interrupted by oxygen, sulfur or N-R; C 4 -C 8 alkenylene or phenylethylene, R 5 and R 6 independently of one another represent a hydrogen atom or a CF 3, C 1 -C 2 alkyl or phenyl residue, or R 5 and R 6 together with the carbon atom to which a C5-C12 cycloalkylidene nucleus which is unsubstituted or substituted by C1-C4 alkyl; with the proviso that when R5 and R6 together represent hydrogen, R4 is different from hydrogen; and with the proviso that when R 1, R 2 and R 2 are simultaneously hydrogen and R 5 and R 6 are at the same time methyl, R 4 is other than hydrogen; R7 represents a hydrogen atom, a C1-C8 alkyl residue or a residue of formula III

H3C CH

N R4 (II;

H3C CH3

  R8 represents a hydrogen atom or a C1-C8 alkyl residue, m is an integer of 2 to 8, and

n represents a number from 2 to 25.

  An alkyl radical having up to 25 carbon atoms means a linear or branched radical such as, for example, a methyl, ethyl, propyl or isopropyl radical,

  n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-

  methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1, 1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,

  tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl.

  One of the preferred meanings of R 1, R 2 and R 4 is, for example, C 1 -C 18 alkyl, in particular C 1 -C 12 alkyl, for example C 1 -C 8 alkyl. A particularly preferred meaning of R 1 and R 2 is methyl and tert-butyl. A meaning

  Particularly preferred is R2 tert-butyl.

  An alkenyl residue of 2 to 24 carbon atoms means a linear or branched residue such as, for example, a vinyl, propenyl, 2-butenyl or 3-butenyl residue,

  isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-

  dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. We

  preferably an alkenyl radical of 3 to 18, in particular of 3 to 12 carbon atoms.

  A C 5 -C 12 cycloalkyl, in particular C 5 -C 8 cycloalkyl, which is unsubstituted or substituted by C 1 -C 4 alkyl, which preferably contains 1 to 3, in particular 1 or 2 linear or branched alkyl radicals, means, for example, a rest

  cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclopentyl,

  hexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cyclohexyl,

  heptyl, cyclooctyl or cyclododecyl. A C5-C8 cycloalkyl residue is preferred,

especially cyclohexyl.

  A phenyl residue substituted with C1-C4 alkyl, which preferably contains

  1 to 3, in particular 1 or 2 alkyl groups, means, for example, a residue o-, m- or p-

  methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl,

  2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-

  ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.

  A C 5 -C 8 cycloalkenyl radical which is unsubstituted or substituted by C 1 -C 4 alkyl, which preferably contains 1 to 3, in particular 1 or 2 linear or branched alkyl radicals, means, for example, a cyclopentenyl or methylcyclopentenyl radical,

  dimethylcyclopentenyl, cyclohexenyl, methylcyclohexenyl, dimethylcyclohexyl

  hexenyl, trimethylcyclohexenyl, tert-butylcyclohexenyl, cycloheptenyl or

  cyclooctenyl. The cyclohexenyl residue is preferred.

  A C 7 -C 6 phenylalkyl residue which is unsubstituted or substituted on the phenyl residue by C 1 -C 4 alkyl, which preferably contains 1 to 3, in particular 1 or 2 linear or branched alkyl radicals, means, for example, a benzyl radical,

  ac-methylbenzyl, α, α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-

  methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-

  tert-butylbenzyl. The benzyl radical is preferred.

  An alkoxy residue having up to 18 carbon atoms means a linear or branched residue such as, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. We prefer a

  alkoxy residue of 6 to 12 carbon atoms.

  A cycloalkoxy radical of 5 to 12 carbon atoms means, for example, a cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy or cyclododecyloxy residue. One of the preferred meanings of R4 is a cycloalkoxy residue

  in C5-C8. Cyclopentyloxy and cyclohexyloxy residues are particularly preferred.

  An alkynyl residue of 3 to 6 carbon atoms means a linear remainder or

  branched as, for example, a propynyl (propargyl) residue (-CH2-C = CH), 2-

butynyl or 3-butynyl.

  An acyl residue of 1 to 8 carbon atoms means, for example, a formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl, benzoyl, acryloyl or crotonyl radical. C1-C8 alkanoyl, alkenoyl radicals are preferred.

  C3-C8 or benzoyl, especially acetyl.

  A C 5 -C 8 cycloalkylidene ring which is unsubstituted or substituted by C 1 -C 4 alkyl, which preferably contains 1 to 3, in particular 1 or 2 linear or branched alkyl radicals, means, for example, a cyclopentylidene, methylcyclopentylidene residue,

  dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclo

  hexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. The residues cyclohexylidene and tertbutylcyclohexylidene are preferred. A C2-C18 alkylene radical means a linear or branched radical such as, for example, an ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene radical. A C2-C12 alkylene radical is preferred, for example alkylene

in C2-C8.

  A C4-C18 alkylene radical interrupted by oxygen, sulfur or / N-Rg can be interrupted one or more times and means, for example

  -CH2CH2-O-CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2-,

  -CH2CH2-N (CH3) -CH2CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2-,

  -CH2CH2- (O-CH2CH2-) 20-CH2CH2-, -CH2CH2- (O-CH2CH2-) 30 -CH2CH2- or

-CH2CH2- (O-CH2CH2-) 40-CH2CH2-.

  When Y or Z is a C4-Cs alkenylene radical, it is for example

remains 2-butenylene-1,4.

  The phenylethylene residue means -CH (C6, H5) CH2-.

  The monomeric compounds of formula I and the oligomeric compounds of formula (IIi) in which R1 and R2 independently of one another are hydrogen or (C1-C18) alkyl, C2-alkenyl are preferred. C18, C5-C8 cycloalkyl, phenyl unsubstituted or substituted with C1-C4 alkyl; C 5 -C 8 cycloalkenyl or C 7 -C 9 phenylalkyl, R 4 represents a hydrogen atom or a C 1 -C 4 alkyl, OH, -CH 2 CN, C 4 -C 8 alkoxy, C 5 -C 12 cycloalkoxy, allyl, propargyl group; C7-C9 acetyl or phenylalkyl;

  A represents an oxygen atom, a residue -C-

R6 He he i

  -CH2CH2-C-O-Y-O-C-CH2CH2- or - (CH) .- O-C-Z-C-O- (CH2), .-

  X represents an oxygen atom or N-R7, Y and Z represent, independently of each other, a C 2 -C 12 alkylene radical, C 4 -C 12 alkylene interrupted by oxygen or / N-R 8; C 4 -C 8 alkenylene or phenylethylene, R 5 and R 6 independently of one another represent a hydrogen atom or a CF 3, C 1 -C 8 alkyl or phenyl radical, or R 5 and R 6 together with the carbon to which they are attached a C5-C8 cycloalkylidene ring; R7 represents a hydrogen atom or a C1-C8 alkyl radical, R8 represents a hydrogen atom or a C1-C4 alkyl radical, m is an integer of 2 to 6, and

n represents a number from 2 to 15.

  The monomeric compounds of formula I and the oligomeric compounds of formula II in which R 1 and R 2 are, independently of one another, a hydrogen atom or a C 1 -C 8 alkyl radical, are also preferred.

cyclohexyl or phenyl.

  The monomeric compounds of formula I and the oligomeric compounds of formula II in which R4 is a hydrogen atom or a C1-C4 alkyl, C4-C16 alkoxy, C5-C8 cycloalkoxy, allyl or propargyl radical are also preferred.

acetyl or benzyl.

  Particularly preferred compounds are the monomeric compounds of formula I and the oligomeric compounds of formula II in which R 1 and R 2 are, independently of one another, a hydrogen atom or a C 1 -C 2 alkyl radical, alkenyl C2-C12, C5-C8 cycloalkyl, phenyl or benzyl, R4 represents a hydrogen atom or a C1-C4 alkyl, C4-C16 alkoxy, C5-C8 cycloalkoxy, allyl, propargyl, acetyl or benzyl;

R5 O O

  wherein X represents an oxygen atom or N-R7, Y and Z represent, independently of one another, an alkylene residue; C2-C8, C4-C12 alkylene interrupted by oxygen or C4-Ce alkenylene, R5 and R6 independently of one another represent a hydrogen atom or a C1-C8 alkyl or phenyl group; or R5 and R6 together with the carbon atom to which they are attached form a C8-C8 cycloalkylidene ring; R7 represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer of 2 to 6, and

n represents a number from 2 to 10.

  Particularly interesting compounds are the monomeric compounds of formula I and the oligomeric compounds of formula II, in which R 1 and R 2 independently of one another represent a hydrogen atom or a C 1 -C 8 alkyl, cyclohexyl or phenyl radical. or benzyl, R4 is hydrogen, C1-C4 alkyl, C6-C12 alkoxy, acetyl or benzyl;

R5 O O

  There is a residue -C-, or -CI 2 CH 2 -COY-OC-CH 2 CH 2 -, R 6 X represents an oxygen atom, Y represents a C 2 -C 8 alkylene radical, C 4 -C 12 alkylene interrupted by oxygen, R5 and R6 represent, independently of one another, a hydrogen atom or a C1-C8 alkyl residue, or else R5 and R6 together with the carbon atom to which they are bonded form a cycloalkylidene ring in the form of C5-C8; and

n represents a number from 2 to 10.

  Compounds having a particularly special interest are the monomeric compounds of formula I and the oligomeric compounds of formula II in which R 1 represents a hydrogen atom, R 2 represents a hydrogen atom or a C 1 -C 4 alkyl or cyclohexyl group, R 3 is a hydrogen atom, R4 represents a hydrogen atom or a C1-C4 alkyl residue, R5 b

A represents a remainder -C-

  R 6 X represents an oxygen atom, R 5 and R 6 represent, independently of each other, a hydrogen atom or a C 1 -C 4 alkyl radical, or R 5 and R 6 together with the atom of carbon to which they are attached a cyclohexylidene ring; and

n represents a number from 2 to 10.

  Particularly preferred compounds are the monomeric compounds of formula I wherein, when R 4 is hydrogen, R 6 and R 6 are

different from hydrogen.

  The monomeric compounds of formula I according to the invention can be prepared in a manner known per se, by analogy with the techniques of the literature mentioned at the beginning. For example, and preferably, a bisphosphorodichloridite of formula IV is reacted with a compound of the HALS type of the formula ## STR1 ## ## STR2 ##

R2 A

  Wherein R 1, R 2, R 3, R 4, A and X have the meanings indicated, to form the compounds

  monomers of formula I according to the invention.

  The HAIS compound of formula V is used in stoichiometric amounts, preferably in a slight excess, with respect to

  bisphosphorodichloridite of formula IV.

  The reaction is carried out in a molten medium or in the presence of a solvent

  organic aprotic, polar or apolar suitable. This reaction takes place preferably

  in the presence of a base at temperatures between -20 C and the point

  boiling the solvent, in particular at temperatures between 10 and 150 C.

  Bases such as, for example, amines, can also be used

at the same time as solvents.

  The base can be used in varying amounts, ranging from catalytic amounts to several times molar excess, through stoichiometric amounts, relative to the compounds of formula IV or V used. The hydrogen chloride formed during the reaction is optionally converted by the base into a chloride which can be separated by filtration and / or washing with a suitable aqueous or solid phase; it is then possible to use a second solvent that is immiscible with water. The isolation of the products is suitably carried out by evaporation of the organic phase and drying of the residue. The products are purified appropriately by

  chromatography on silica gel or by recrystallization.

  Suitable solvents for carrying out the reaction are, inter alia, hydrocarbons (for example mesitylene, toluene, xylene, hexane, pentane or other petroleum ether fractions), halogenated hydrocarbons ( for example di- or trichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane or chlorobenzene), ethers (for example diethyl ether, dibutyl ether or tetrahydrofuran), ketones (for example acetone, ethylmethylketone, diethylketone, methylpropylketone or cyclohexanone), or else acetonitrile,

  butyl acetate, dimethylformamide, dimethylsulfoxide or N-

  methylpyrrolidone. Suitable bases are, inter alia, primary, secondary and especially tertiary amines (for example trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline or pyridine), hydrides (for example hydride). of lithium, sodium, potassium) or alcoholates (eg

for example sodium methoxide).

  When hydrides (for example sodium hydride, sodium borohydride or lithium aluminum hydride), alkali metals, alkali hydroxides or sodium methylate are used as the bases, it is possible to form first, the corresponding alkoxide of the HALS compound of formula V; the reaction product which is optionally formed under these conditions (for example water, methanol) is distilled off (for example in the form of an azeotrope with

  toluene) before the reaction with the bisphosphorodichloridite of formula IV.

  The compounds of formula IV are known or can be prepared by methods known per se, as described for example in DE-A-3 928 291 or by RA. Bartlett et al., J. Amer. Chem. Soc. 109 (19)

5699 (1987).

  The compounds of formula IV required for the preparation of the compounds of formula I according to the invention can be prepared in situ by analogy with the techniques of the literature mentioned above and then reacted without isolating them with the HALS-type compounds of formula V to form the monomeric compounds of formula I. The HALS compounds of formula V are known or can be prepared by methods known per se, as described for example in US-A-4,233 412. Oligomeric compounds of formula II according to the invention can be prepared

  by analogy to the monomeric compounds of formula I described above.

  Another subject of the invention is a preferred process for the preparation of the oligomeric compounds of formula II, characterized in that a bisphenol of formula VI or a mixture of bisphenols of formula VI is first reacted first.

R1 R

HO NOH

2I I -4 (VI)

R3 R3

  in which R 1, R 2, R 3 and A have the meanings indicated, with phosphorus trichloride to give a compound of formula VII C 1 R 1 Cl a A (VII) C f R 2 A R 2

R3 R3

  Wherein R1, R2, R3, n and A have the meanings indicated; and then the compound of formula VII is reacted with an HALS compound of formula V or a mixture of HALS compounds of formula V H HX1 CA

HX N-R4 (V)

7CH 3 CA

  in which R4 and X have the indicated meanings.

  The preferred reaction conditions for the second reaction step (reaction with the HALS compound of formula V), for example the temperature, the solvent, the base or the catalyst, correspond to those already described above for

  the monomeric compounds of formula I according to the invention.

  The reaction of bisphenol of formula VI with phosphorus trichloride to form the oligomeric compound of formula VII is carried out in a molten medium or in the presence of a suitable aprotic, polar or apolar organic solvent. This reaction is preferably carried out in the presence of a base or a phase transfer reagent at temperatures of between 20 ° C. and the boiling point of the solvent, in particular at temperatures of between 20 ° C. and 150 ° C. for example between 40 C

and 120 C.

  Suitable solvents for carrying out the reaction are, inter alia, hydrocarbons (for example mesitylene, toluene, xylene, hexane, pentane or other petroleum ether fractions), halogenated hydrocarbons ( for example di- or trichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane or chlorobenzene), ethers (for example diethyl ether, dibutyl ether or tetrahydrofuran), ketones (for example acetone, ethylmethylketone, diethylketone, methylpropylketone or cyclohexanone), or else acetonitrile,

  butyl acetate, dimethylformamide, dimethylsulfoxide or N-

  methylpyrrolidone. The preferred solvents are hydrocarbons, in particular

toluene and xylene.

  The base or phase transfer reagent is preferably used in catalytic amounts relative to the bisphenol of formula VI used. The catalyst is preferably used in an amount of from 1 to 10 mol%, in particular from 2 to

  8 mol%, relative to the bisphenol of formula VI used.

  Suitable bases are, inter alia, tertiary amines, for example trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline,

  N, N-diethylaniline, pyridine or 4-dimethylaminopyridine. 4-

  dimethylaminopyridine is particularly preferred.

  Suitable phase transfer reagents are, for example, quaternary ammonium salts such as, for example, tetrabutylammonium chloride or tetrabutylammonium bromide. Tetrabutylammonium bromide is

especially preferred.

  The structural composition of the oligomeric compounds of formula VII depends on the reaction conditions, for example the solvent or the temperature of the reaction, as well as the molar ratio and the concentration of the bisphenol of

  formula VI and phosphorus trichloride.

  Preferred molar ratios of bisphenols of formula VI to phosphorus trichloride are from 1: 1 to 1: 5. In particular, a

  molar ratio of between 1: 1 and 1: 3.

  Oligomeric compounds of formula VII are preferably not isolated.

  After the end of the reaction with the phosphorus trichloride, the excess phosphorus trichloride is distilled off, advantageously with a part of the solvent. The solution of the oligomeric compounds of formula VII is then reacted with an HALS compound of formula V to form the compounds of formula II.

according to the invention.

  Preferred molar ratios of the bisphenols of formula VI to the HALS compounds of formula V for the preparation of the oligomeric compounds of formula II according to the invention are between 1: 1 and 1: 6, in particular between 1: 1,2

  and 1: 5, for example between 1: 1: 4 and 1: 4.4.

  The monomeric and oligomeric compounds of formula I and II according to the invention are suitably isolated by filtration of the precipitated salts of the bases used and

  evaporation of the filtrate under reduced pressure.

  Filtration auxiliaries, for example, are preferably used for

  celite, silica gel, diatomaceous earth or aluminum silicate.

  In order to fully precipitate the ammonium salts, the filtered filter residue is preferably taken up again in a non-polar solvent such as, for example, toluene / hexane and filtered again. The HALS compound of formula V in excess is preferably removed by distillation under

reduced pressure.

  Bisphenols of formula VI are known or can be prepared according to

  Houben-Weyl, Methoden der organischen Chemie, volume 6 / lc, 1030.

  As already indicated, the HALS compounds of formula V are known or can be prepared according to methods known per se, as they are

  described for example in US-A-4,233,412.

  The two-step process described above preferably gives

  mixtures of oligomeric compounds of formula II.

  The present invention thus also relates to oligomeric products obtainable by reacting a bisphenol of formula VI or a mixture of bisphenols of formula VI with phosphorus trichloride and a HALS compound of formula V or a mixture of compounds. of the HALS type of formula V. The oligomeric compounds of formula II according to the invention may be linear or cyclic, as represented by formula VIII,

H3C N CH3

RCt -C

R1 X

  IX or a radical of formula X m (mX R / -Xl- - P-R-X X

IN __P_

  the terminal group E 1 preferably contains a chlorine atom or a remainder of the formula X ic CH 3 C (I x) R-X 2 R 4 (xi)

I C

  In the terminal group E 1 represents the prefet of Pchloeo, a remainder of the formula XI-R4 -R4 R (i) X or the terminal groups E1 and E2 together form a direct link

  (cyclic compounds), R4 and X having the indicated meanings.

  Oligomeric compounds of formula VIII in which E1 is preferred

  represents a radical of formula IX and E2 represents a radical of formula XI.

  The monomeric and oligomeric compounds of formulas I and II according to the invention are suitable as stabilizers for organic materials against degradation induced by oxidation, heat or light. Examples of such materials are: 1. polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly (4-methylpentene-1), polyisoprene or polybutadiene and polymers of cycloolefins as for example cyclopentene or norbornene; or else polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE),

  low density branched polyethylene (VLDPE).

  The polyolefins, namely the polymers of monoolefins, which are mentioned by way of example in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various processes, in particular by the following methods: a) by a radical route ( usually under high pressure and at high temperature); b) using a catalyst, the catalyst usually containing one or more metals of groups IVb, Vb, VIb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyl, alkenyl and / or aryl groups, which may have a 7X coordination type or a. These metal complexes can be free or fixed on a support, for example on activated magnesium chloride, titanium (II) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization, or other activators can be used such as, for example, alkyl metal compounds, metal hydrides, alkyl metal halides, alkyl metal oxides or metal alkyloxanes, the metals being elements of groups Ia, IIa and / or Ila. Activators may for example be modified with other ester, ether, amine or silyl ether groups. These catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene catalysts

  or SSC (Single Site Catalyst).

  2. mixtures of polymers listed under 1., for example mixtures of polypropylene and polyisobutylene, polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene

(for example LDPE / HDPE).

  Copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, copolymers

  ethylene-heptene, ethylene-octene copolymers, propylene-

  butadiene, isobutylene-isoprene copolymers, ethylene-acrylate copolymers

  of alkyl, ethylene-alkyl methacrylate copolymers, ethylene-

  vinyl acetate and copolymers thereof with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbornene ; or mixtures of such copolymers with each other or with polymers mentioned under 1., for example polypropylene / ethylene-propylene copolymer mixtures, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene copolymers vinyl acetate, LLDPE / ethylene-acrylic acid copolymers and copolymers with alternating or random polyalkylene / carbon monoxide structure and mixtures thereof with other polymers such as, for example, polyamides; 4. hydrocarbon resins (for example C5-C9) including their hydrogenated derivatives (for example adhesive resins) and mixtures of polyalkylenes and starch; 5. polystyrene, poly (p-methylstyrene), poly (α-methylstyrene); 6. copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives such as, for example, styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-acrylate and methacrylate copolymers; alkyl, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; high resiliency blends of styrene copolymers and another polymer such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and styrene block copolymers such

  that, for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-

  ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

  7. Graft copolymers of styrene or α-methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; of styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or poly (alkyl methacrylates), styrene and acrylonitrile-on acrylate-butadiene copolymers, as well as their mixtures with the copolymers listed under 6., known for example under the name of

ABS, MBS, ASA or AES polymers.

  8. halogenated polymers such as polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and copolymers of epichlorohydrin, in particular polymers of halogenated vinyl compounds such as for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; as well as their copolymers such as, for example, vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate copolymers; 9. polymers derived from α, β-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, modified poly (methyl methacrylates) with high impact resistance with butyl acrylate,

  polyacrylamides and polyacrylonitriles.

  10. Copolymers of the monomers mentioned under 9. between them or with other unsaturated monomers such as, for example, acrylonitrile-butadiene copolymers,

  acrylonitrile-alkyl acrylate copolymers, acrylonitrile copolymers,

  alkoxyalkyl acrylate, acrylonitrile vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers; 11. polymers derived from alcohols and unsaturated amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, poly (vinyl benzoate), polyvinyl maleate, polyvinylbutyral, poly (allyl phthalate), polyallylmelamine, and copolymers thereof with the olefins mentioned in point 1; 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, poly (propylene oxide) or copolymers thereof with bisglycidyl ethers; 13. polyacetals, such as polyoxymethylene, and polyoxymethylenes which contain comonomers such as, for example, ethylene oxide; polyacetals which are modified with thermoplastic polyurethanes, acrylates or MBS; 14. polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides; 15. polyurethanes which are derived from polyethers, polyesters or polybutadienes having terminal hydroxyl groups and from aliphatic or aromatic polyisocyanates and their precursors; 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9 , 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides based on m-xylene, a diamine and adipic acid; polyamides prepared from hexamethylenediamine and iso- and / or terephthalic acid and optionally

  elastomer as modifying agent, for example poly (2,4,4-trimethylhexane)

  methyleneterephthalamide) or poly (m-phenylene isophthalamide), block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol; or alternatively polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during shaping ("RIM polyamide systems"); 17. polyureas, polyimides, polyamide-imides and polybenzimidazoles; 18. polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, such as poly (terephthalate)

  ethylene), poly (butylene terephthalate), poly (1,4-terephthalate)

  dimethylolcyclohexane), polyhydroxybenzoates and copolyethers

  block esters derived from polyethers having terminal hydroxy groups; or alternatively polyesters modified with polycarbonates or MBS; 19. polycarbonates and polyestercarbonates;

  Polysulfones, polyethersulfones and polyetherketones.

  21. Cross-linked polymers which derive from aldehydes on the one hand and from

  phenols, ureas or melamines, such as phenol-formaldehyde resins, urea-

  formaldehyde and melamine formaldehyde; 22. drying and drying non-drying alkyd resins; 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols, and vinyl compounds

  as crosslinking agents, as well as their halogenated derivatives which are not very inflammable.

  Crosslinkable acrylic resins derived from substituted acrylic esters such as epoxy acrylates, urethane acrylates or polyester acrylates; 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, polyisocyanates or epoxy resins; 26. cross-linked epoxy resins derived from polyepoxides, for example

  bis-glycidyl ethers or cycloaliphatic diepoxides.

  27. Natural polymers such as cellulose, natural rubber, gelatines, and their chemically modified derivatives of homologous polymers, such as cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose; as well as rosin resins and their derivatives; 28. blends (polyblends) of the aforementioned polymers, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and its copolymers, PA / HDPE, PA / PP, PA / PPO; 29. Natural and synthetic organic substances which are pure monomeric compounds or mixtures of these compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or synthetic ester oils, waxes and greases (for example phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic esters with mineral oils in any mass proportions, such as those which can be used for example as spinning preparations, as well as as their aqueous emulsions; 30. aqueous emulsions of natural or synthetic rubbers, such as

  for example, natural rubber latex or styrene copolymer latexes

carboxylated butadiene.

  Other objects of the invention are therefore also compositions containing (a) an organic material exposed to degradation due to oxidation, heat or light and (b) at least one monomeric or oligomeric compound of formula I or II, or at least one oligomeric product obtainable by reaction of a bisphenol of formula VI or a mixture of bisphenols of formula VI with phosphorus trichloride and a HALS compound of formula V or a mixture of HALS type of formula V. As regards the organic materials to be protected, it is preferably natural, semi-synthetic or preferably synthetic organic materials. Thermoplastic polymers, in particular PVC or polyolefins, especially polyethylene and polypropylene, are particularly preferred. It is necessary to underline in particular the activity of the compounds according to the invention against degradation by heat and oxidation, especially in the case of thermal stress, such as that which occurs at the time of shaping thermoplastics. The compounds according to the invention are therefore especially suitable

  for use as shaping stabilizers.

  The monomeric and oligomeric compounds of formula I and IIH are preferably added to the material to be stabilized in amounts of from 0.01 to 10%, for example from 0.01 to 5%, preferably from 0.025 to 3%, in particular from 0, 025 to 1%, compared to

  the mass of the organic matter to be stabilized.

  In addition to the monomeric and oligomeric compounds of formulas I and II, the compositions according to the invention may contain other costabilizers such as, for example: 1. Antioxidants 1.1. alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol,

  2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6di-tert-

  butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-

  dicyclopentyl-4-methylphenol, 2- (act-methylcyclohexyl) -4,6-dimethylphenol,

  2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditert-

  butyl-4-methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-

  6- (1'-methyl-11'-undecyl) phenol, 2,4-dimethyl-6- (1'-methyl-heptadecyl) -

  phenol, 2,4-dimethyl-6- (1'-methyl-1'-tridecyl) phenol and mixtures thereof.

  1.2. alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6tert-

  butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-

Ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

  1.3. hydroquinones and hydroquinones alkvlées, for example 2,6di-tert-

  butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tertamyl-

  hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-

  butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tertbutyl-4-

  hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate. 1.4. tocopherols. for example, α-tocopherol,--tocopherol, ytocopherol, 5-tocopherol and mixtures thereof (vitamin E).

  1.5. hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-

  methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tertbutyl-3-

  methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'thiobis (3,6-

  di-sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

  1.6. alkylidenebisphenols, for example 2,2'-methylenebis (6-tertbutyl-4-

  methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-

  methylenebis [4-methyl-6- (at-methylcyclohexyl) phenol], 2,2'-methylenebis (4-

  methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol),

  2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol)

  butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-

  methylenebis [6- (at-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6 (act, a-

  dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tertbutylphenol),

  4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-

  2-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxyethyl)

  benzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methyl-

  phenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-ndodecyl-

  mercaptobutane, bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate]

  of ethylene glycol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopenta

  diene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-

  butyl-4-methylphenyl], 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-dodecylmercaptobutane, the 1,1,5,5-tetra (5tert-

  butyl-4-hydroxy-2-methylphenyl) pentane.

  1.7. O- compounds. N- and S-benzylated e.g. 3,5,3 'oxide, 5'tratra-tert-

  butyl-4,4'-dihydroxydibenzyl, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, dithioterephthalate

  of bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), bis (3,5-di-tert-

  butyl-4-hydroxybenzyl), isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

  1.8. hydroxybenzyl malonates, for example 2,2-bis (3,5-di-tertbutyl-2-

  hydroxybenzyl) dioctadecyl malonate, 2- (3-tert-butyl-4-hydroxy-5-

  dioctadecyl methylbenzyl) malonate, 2,2-bis (3,5-di-tert-butyl) -4-

  hydroxybenzyl) didodecylmercaptoethyl malonate, 2,2-bis (3,5-ditert-butyl)

  Di [4- (1,1,3,3-tetramethylbutyl) phenyl] 4-hydroxybenzyl) malonate].

  1.9. hydroxybenzylated aromatic compounds, for example 1,3,5-triis (3,5-di-

  tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-ditert-butyl)

  4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tertbutyl-4-

hydroxybenzyl) phenol.

  1.10. triazine compounds, for example 2,4-bis-octylmercapto-6 (3,5-di-

  tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6bis (3,5-di-

  tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6bis (3,5-di-

  tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tertbutyl-4-

  hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4hydroxy-

  benzyl) 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) hexahydro-1,3,5-

  triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

  1.1i. benzylphosphonates, for example 2,5-di-tert-butyl-4-hydroxy-

  dimethyl benzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzyl-

  diethyl phosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-ditert-butyl calcium salt -4-hydroxybenzylphosphonate monoethyl. 1.12. acylaminophenols, for example 4-hydroxyanilide of lauric acid,

  4-hydroxyanilide of stearic acid, N- (3,5-di-tert-butyl-4-

hydroxyphenyl) octyl carbamate.

  1.13 esters of B- (3,5-di-tert-butyl-4hydroxyphenyl) propionic acid with mono- or polyalcohols, for example with methanol, ethanol, octanol,

  octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-

  propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,

  triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N-

  bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

  trioxabicyclo [2.2.2] octane. 1.14. esters of 3- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, , 6-hexanediol, 1,9-nonanediol, ethyleneglycol, 1,2-propanediol, neopentylglycol, thiodiethyleneglycol, diethyleneglycol,

  triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-

  bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

  trioxabicyclo [2.2.2] octane. 1.15. esters of B- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyalcohols, for example with methanol, ethanol or octanol,

  octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-

  propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,

  triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-

  bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

  trioxabicyclo [2.2.2] octane. 1.16. esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyalcohols, for example with methanol, ethanol or octanol,

  octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-

  propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,

  triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-

  bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

  trioxabicyclo [2.2.2] octane. 1.17. amides of 5- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid by

  for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene

  diamine, N, N'-di- (3,5-di-tert-butyl-4hydroxyphenylpropionyl) trimethylene

  diamine, N, N'-di- (3,5-di-tert-butyl-4hydroxyphenylpropionyl) hydrazine.

  2. UV absorbers and light stabilizers.

  2.1. 2- (2'-hydroxyphenyl) benzotriazoles. for example 2- (2-hydroxy-5'-

  methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2-hydroxyphenyl) benzo

  triazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5'-

  (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tertbutyl-2'-

  hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methyl)

  phenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2-hydroxybutyl)

  phenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2-

  (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (α, α-dimethyl)

  benzyl) -2'-hydroxyphenyl) benzotriazole, a mixture of 2- (3'-tert-butyl) -2-

  hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2 (3'-

  tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5chloro-

  benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) -

  phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxy)

  carbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-

  octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-

  ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl)

  2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2-hydroxy-5 '

  (2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2'-methylenebis [4 (1,1,3,3-

  tetramethylbutyl) -6- (benzotriazole-2-yl) phenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2-hydroxyphenyl] benzotriazole

  with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 12- with R = 3'-tert-butyl-

  4'-hydroxy-5 '- (2H-benzotriazole-2-yl) phenyl. 2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy derivatives,

  4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-

hydroxy-4,4'-dimethoxy derivatives.

  2.3. optionally substituted benzoic acid esters, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tertbutylbenzoyl) resorcinol,

  benzoylresorcinol, 2,4-di-tert-butyl-4-hydroxybenzoate

  butylphenyl, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-

  octadecyl butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4hydroxybenzoate. 2.4. acrylates for example ethyl-3-cyano-3,4-diphenylacrylate or

  of isooctyl, methyl α-carbomethoxycinnamate, ca-cyano-3-methylp-

  methyl or butyl methoxycinnamate, c-carbomethoxy-p-

  methyl methoxycinnamate, N- (B-carbomethoxy-13-cyanovinyl) -2-

methylindoline.

  2.5. nickel compounds. for example nickel complexes with 2,2'-

  thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 complex or the 1: 2 complex, with optional additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dithiocarbamate

  dibutylnickel, nickel salts of monoalkyl esters of 4-hydroxy-3,5-

  di-tert-butylbenzylphosphonic acid, such as methyl or ethyl esters,

  Nickel complexes with ketoximes such as 2-hydroxy-4-

  methylphenylundecylketoxime, nickel complexes with 1-phenyl-4-

  lauroyl-5-hydroxypyrazole, optionally with other ligands.

  2.6. sterically hindered amines, for example bis (2, 2,6,6-

  tetramethylpiperidyl), bis (2,2,6,6-tetramethylpiperidyl) succinate, sebacate

  bis (1,2,2,6,6-pentamethylpiperidyl), n-butyl-3,5-di-tert-butyl-4-

  bis (1,2,2,6,6-pentamethylpiperidyl) hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and

  succinic acid, the condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-

  piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5

  triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, 1,2,3,4-

  butanetetracarboxylate of tetrakis (2,2,6,6-tetramethyl-4-piperidyl), 1,1 '- (1,2-

  ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-

  methylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 2-nbutyl-2-

  Bis (1,2,2,6,6-pentamethyl) (2-hydroxy-3,5-di-tert-butylbenzyl) malonate

  piperidyl), 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4. 5] decane-2,4

  dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, the condensation product of

  N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-

  morpholino-2,6-dichloro-1,3,5-triazine, the condensation product of 2-chloro

  4,6-di (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-

  bis (3-aminopropylamino) ethane, the condensation product of 2-chloro4,6-

  di (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-

  aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1, 3, 8-

  triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-

  piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-

  piperidyl) pyrrolidine-2,5-dione. 2.7. diamides of oxalic acid, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide,

2,2'

  didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-

  bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tertbutyloxanilide and mixtures of oxanilides disubstituted with methoxy at o and p, and with ethoxy at o and p.

  2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines, for example 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) -4,6bis (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-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) 4,6-

  bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-

  butyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, the 2- [2-

  hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl-

  phenyl) -1,3,5-triazine. 3. Metal deactivators, for example N, N'-diphenyloxamide, N-

  salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-

  di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-

  triazole, oxalic acid bis (benzylidene) dihydrazide, oxanilide, dihydrazide

  isophthalic acid, bis (phenylhydrazide) of sebacic acid, N, N'-

  diacetyldihydrazide of adipic acid, the acid N, N'-bissalicyloyldihydrazide

  oxalic acid, the N, N'-bis-salicyloyldihydrazide of thiopropionic acid.

  4. Phosphites and phosphonites such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri (nonylphenyl) phosphite, trilauryl phosphite, phosphite

  trioctadecyl, distearylpentaerythritol diphosphite, tris (2,4-di-

  tert-butylphenyl), diisodecylpentaerythritol diphosphite, diphosphite

  bis (2,4-di-tert-butylphenyl) pentaerythritol, diphosphite bis (2,6-di-tert-butyl-

  4-methylphenyl) pentaerythritol, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tertbutylphenyl) pentaerythritol diphosphite, triphosphite tristearyl sorbitol,

  diphosphonite of tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylylene, 6-

  isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2dioxaphosphocine,

  6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphospho

  cine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite,

  bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite.

  5. Compounds that destroy peroxides, for example esters of 3-

  thiodipropionic, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole,

  dibutylzinc dithiocarbamate, dioctadecyl disulfide, tetrakis (3-

  dodecylmercapto) pentaerythritol propionate.

  6. Polyamide stabilizers, for example copper salts in combination

  with iodides and / or phosphorus compounds and salts of divalent manganese.

  7. Basic costabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Ricinoleate

  Na, K palmitate, antimony pyrocatecholate or tin pyrocatecholate.

  8. Nucleating agents, for example 4-tert-butylbenzoic acid, the acid

  adipic, diphenylacetic acid.

  9. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, sulphate

  barium, metal oxides and hydroxides, carbon black, graphite.

  10. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents,

blowing agents.

  11. Benzofuranones or indolinones, as described, for example, in

  US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-

  216,052, US-A-5,252,643, DE-A-4,316,611, DE-A-4,316,622, DE-A-

  4316,876, EP-A-0 589 839 or EP-A-0 591 102, or 3- [4- (2-

  acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tertbutyl-

  3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-ditert-

  butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3-

  (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-

  di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) 5,7-

di-tert-butylbenzofurane-2-one.

  The costabilizers, with the exception of the benzofuranones described in point 11, are added for example to concentrations of 0.01 to 10% with respect to

  total mass of the material to be stabilized.

  Other preferred compositions contain, in addition to component (a) and monomeric and oligomeric compounds of formula I and II, further other additives, in particular phenolic antioxidants, light stabilizers and / or

shaping stabilizers.

  Particularly preferred additives are phenolic antioxidants (point 1 of the list), sterically hindered amines (point 2.6 of the list), phosphites and phosphonites (point 4 of the list) and compounds which destroy the

peroxides (point 5 of the list).

  Other particularly preferred additives (stabilizers) are benzofuran-2-ones as described, for example, in US-A-4,325,863, US-A-4,338,244, US Pat. 5,175,312, US-A-5,216,052,

  US-A-5,252,643, DE-A-4,316,611, DE-A-4,316,622, DE-A-4,316,876, EP-A-

0 589 839 or EP-A-0 591 102.

  Examples of such benzofuran-2-ones are compounds of the formula

R'14 R'15

A <eO R'15

P R'2 H R ', 1

  wherein R'11 represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system; R'12 is a hydrogen atom; R'14 represents a hydrogen atom or an alkyl radical of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chloro; R'13 has the meaning of R'12 or R'14 or represents a remainder of formula

O 0 0 O

  ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ##

O O O O

  ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ## N NC- (CH 2), -CH 2 -S-R '19, -CH (C 6 H 5) -C-OR' 16 or -DE, where R '16 is a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, alkyl of 2 to 18 carbon atoms interrupted by oxygen or sulfur, dialkylaminoalkyl having in all 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl substituted with 1 to 3 alkyl radicals having a total of up to 18 carbon atoms, s is 0, 1 or 2, the R'17 substituents are independently of one another a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl , phenyl, phenyl substituted with 1 or 2 alkyl radicals having in total up to 16 carbon atoms, an OI radical of formula -C2I'OH, -C2I4-O-CH or -C2H; OC-R'20 or together of formula -C, 2H40H, -C.2H4 -O-CH2 ,,, or -C2Hi -OO-C-R'2, or together with the nitrogen atom to which they are attached form a piperidine residue; or morpholine; t is a number from 1 to 18; R'w is a hydrogen atom or an alkyl residue of 1 to 22 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; A represents an alkylene radical of 2 to 22 carbon atoms optionally interrupted by nitrogen, oxygen or sulfur; R'18 is a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted with 1 or 2 alkyl radicals having in total up to 16 carbon atoms or benzyl; R'19 represents an alkyl radical of 1 to 18 carbon atoms; D is -O-, -S-, -SO-, -SO2- or -C (R'21) 2-; the R'21 substituents represent, independently of one another, a hydrogen atom or a C1-C12 alkyl residue, the two R'21 residues containing together 1 to 16 carbon atoms, and R'21 is also a phenyl radical or a radical of formula

O O

  II (CH 2 'C-OR' m, or - (CH 2) C N (R '17) 2, o s, R' 16 and R '17 have the meanings given above, E is a radical of formula

R14X, 0

R 'R

R, 125

  I o, laqele '1,' 1 etR'4 ntle R1,2 H PRl1 wherein R'1l, R'12 and R'14 have the meanings given above; and R'15 represents a hydrogen atom or an alkyl residue of 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chloro or a residue of formula -CH2-C-OR ', 6 or O il -CHI-CN (R'17) 2 o R'16 and R'17 have the meanings given above, or else

  R'zs forms with R'14 a tetramethylene residue.

  Benzofuran-2-ones in which R '13 represents a hydrogen atom or an alkyl radical of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chloro, or a radical of the formula (CH2-C-OR'), are preferred. I6 - (CH2JC-N (R'17) 2, or -DE, os, R'16 and R'17, D and E have the meanings given above, R'16 having in particular the meaning of a hydrogen atom

  or an alkyl residue of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

  Benzofuran-2-ones in which R11 is a phenyl or phenyl radical substituted by 1 or 2 alkyl radicals having up to 12 carbon atoms are further preferred; R'12 is a hydrogen atom; R'14 is a hydrogen atom or an alkyl residue of 1 to 12 carbon atoms; R'13 is a hydrogen atom or an alkyl residue of 1 to 12 carbon atoms, --CH (-C-OR'16, O1- (CH1) CN (R'17) 2, or - DE; R'15 is a hydrogen atom or an alkyl residue of 1

O O

  It has 20 carbon atoms, -CH2-C-OR'16 or -CH2-C-N (R'17) 2 or R'15 forms with R'14 a tetramethylene residue, s, R'16, R '17, D and E having the given meanings

initially.

  Benzofuran-2-ones also of particular interest are those in which R '13 represents a hydrogen atom or an alkyl radical of 1 to 12 carbon atoms or -D-E; R'12 and R'14 are independently of one another a hydrogen atom or an alkyl residue of 1 to 4 carbon atoms; and R'15 represents an alkyl radical of 1 to 20 carbon atoms, D and E having the meanings given initially.

  Finally, there is a special emphasis on the value of benzofuran

  2-ones wherein R'13 represents an alkyl radical of 1 to 4 carbon atoms or -D-E; R'12 and R'14 are a hydrogen atom; and R'15 represents an alkyl radical of 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D being a group -C (R'21- and E a radical of formula

R'14 / R15

R 14> O

  R 12 o the substituents R'21 are identical or different from each other and each represent an alkyl residue of 1 to 4 carbon atoms, and R'11, R'12, R'14 and R'15 have the

indicated meanings.

  The amount of benzofuran-2-ones added may vary within wide limits. They may be contained, for example, in amounts of from 0.0001 to 5, preferably from 0.001 to 2, in particular from 0.01 to 2% by weight, in the compositions

according to the invention.

  The incorporation of the monomeric and oligomeric compounds of formulas I and II and optionally other additives into the polymer organic material is carried out according to known methods, for example before or during the shaping or by application of the compounds in solution or in dispersion on the polymeric organic material, optionally followed by evaporation of the solvent. The compounds of formula I and II according to the invention can also be added to the materials to be stabilized in the form of a masterbatch which contains them, for example, at a concentration of

2.5 to 25% by weight.

  It is also possible to add the monomeric and oligomeric compounds of formula I

  and HI according to the invention before or during the polymerization or before the crosslinking.

  The monomeric and oligomeric compounds of formula I and II may be incorporated into the material to be stabilized in pure form or in encapsulated form in

  waxes, oils or polymers.

  The monomeric and oligomeric compounds of formula I and II can also be sprayed on the polymer to be stabilized. They are able to dilute other additives (for example the usual additives indicated above) or their melts, so that they can also be sprayed at the same time as these additives on the polymer to be stabilized. The spray addition during the deactivation of the polymerization catalysts is particularly advantageous, the steam used

  for deactivation, which may for example be used for spraying.

In the case of polyolefins polymerized in the form of beads, it may for example be advantageous to apply the compounds of formula I and II according to the invention.

  by spraying, possibly together with other additives.

  The materials thus stabilized can be used in the most varied forms, for example in the form of sheets, fibers, strips, molding materials, profiles or as binders for paints, adhesives or cements. As mentioned above, it is preferably, as regards the organic materials to be protected, organic polymers, in particular synthetic polymers. Here thermoplastics, in particular polyolefins, are particularly advantageously protected. It is especially important to emphasize the excellent activity of the compounds of formula I as forming stabilizers (heat stabilizers). For this purpose, they are advantageously added to the polymer before or during its shaping. But it is also possible to stabilize other polymers (for example elastomers) or lubricants or hydraulic fluids against degradation, for example the degradation induced by light or the oxidation and the heat. Elastomers are to be taken in the above enumeration of materials

organic possible.

  Lubricants and hydraulic fluids to be considered are for example based on mineral or synthetic oils or their mixtures. Lubricants are well known to those skilled in the art and are described in the relevant specialist literature, for example in Dieter Klamann, "Schmierstoffe und verwandte Produkte" (Chemie Editions, Weinheim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch "(Editions Dr. Alfred H thig, Heidelberg, 1974) and in" Ulmanns Enzyklopadie der technischen Chemie ", volume 13, pages 85-94

(Chemie Editions, Weinheim, 1977).

  A preferred embodiment of the present invention is thus the use of monomeric and oligomeric compounds of formula I and II and products obtainable by reaction of a bisphenol of formula VI or a mixture of bisphenols of formula VI with phosphorus trichloride and an HALS compound of formula V or a mixture of HALS compounds of formula V for the stabilization of organic materials against oxidation-induced degradation,

heat or light.

  The monomeric and oligomeric compounds of formula I and II according to the invention are distinguished by a very good stability to hydrolysis and advantageous coloring properties, namely a low coloring of organic materials.

during treatment.

  Organic materials stabilized with the compounds of the present invention are particularly well protected against light-induced degradation. The present invention also relates to a method of stabilizing an organic material against degradation due to oxidation, heat or light, characterized in that it is incorporated in this material or in that it is applied on this material at least one monomeric or oligomeric compound of formula I or II or a product obtainable by reaction of a bisphenol of formula VI or a mixture of bisphenols of formula VI with phosphorus trichloride and a compound of the type HALS of formula V or a mixture of HALS compounds of formula V. The following examples explain the invention in more detail. The

  data in parts or percentages refer to the mass.

  Example 1: Preparation of the compound (101) (Table 1).

  a) in a 15.22 g (40.0 mmol, 1.0 equivalent) nitrogen-stirred suspension of 4,4'-cyclohexylidene-bis (2-tert-butylphenol) and 0.20 g (1 60 mmol) of 4-dimethylaminopyridine in 46 ml of toluene is added dropwise at room temperature 9.10 ml (14.28 g, 104 mmol, 2.6 equivalents) of phosphorus trichloride. It is then heated at 100 ° C. in one hour and stirred for 1.5 hours at this temperature. After stopping the evolution of hydrochloric gas, stirring is continued at 100 ° C. for 30 minutes under a slight stream of nitrogen. The solution obtained is diluted with 20 ml of toluene and the phosphorus trichloride is distilled off.

  excess at the same time as about 20 ml of toluene. The solution contains 4,4'-

  cyclohexylidene bis (2-tert-butylphenyl dichlorophosphite).

  b) In a suspension stirred under a nitrogen atmosphere of 27.4 g (175 mmol, 4.4 equivalents) of 2,2,6,6-tetramethylpiperidin-4-ol and 22.2 g (220 mmol; 5 equivalents) of triethylamine in 250 ml of toluene, the solution described above (Example 1a) was added dropwise in 10 minutes at room temperature. The reaction mixture is then heated to 105 ° C. and stirred for 5 hours at this temperature. The white slurry is cooled to room temperature, filtered through celite and the filtrate concentrated by rotary evaporation in vacuo. The residue is taken up in a hexane / toluene solvent mixture = 1: 1 and filtered again on celite. The filtrate is concentrated by rotary evaporation in vacuo and the residue is dried under high vacuum. We obtain

  17.84 g (42%) of the compound (101), mp 48-52 ° C (Table 1).

  Example 2: Preparation of the compound (102) (Table 1).

  In a similar manner to Example 1, starting from 23.2 g (40.0 mmol, 1.0 equivalent) of 4,4'-cyclohexylidene bis (2-tertbutylphenyl dichlorophosphite) (Example la) in 50 ml. of toluene and 27.4 g (160 mmol, 4.0 equivalents) of 1,2,2,6,6-pentamethylpiperidin-4-ol, 23.7 g (53% o) of the compound (102) are obtained. ,

  melting point 51-57 ° C (Table 1).

  Example 3: Preparation of the Oligomeric Compound (103) (Table 2) a) In a 7.85 g (20.0 mmol, 1.0 equiv) 2,2-bis (3-) stirred suspension under a nitrogen atmosphere cyclohexyl-4-hydroxyphenyl) propane and 0.20 g (1.60 mmnole) of 4-dimethylaminopyridine in 15 ml of toluene are added dropwise at 50 ° C. 4.55 ml (7.10 g, 52 mmol; , 6 equivalents) of phosphorus trichloride. After about 30 minutes, the mixture is heated to 75 ° C. and stirred for 1.5 hours at this temperature. The reaction mixture is then concentrated on the evaporator

  rotary vacuum and the residue (9.14 g) dissolved in 50 ml of toluene.

  b) In a suspension stirred under a nitrogen atmosphere of 9.14 g (20 mmol, 1.0 equivalent) of bisdichlorophosphite (see above, Example 3a) in ml of toluene, is added dropwise, in 15 minutes, a solution of 55 g (61.6 mmol, 3.1 equivalents) of 1,2,2,6,6-pentamethylpiperidine-4-ol and 8.57 g (84.7 mmol; 2 equivalents) of triethylamine in 100 ml of toluene. The reaction mixture is then heated to 105 ° C. and stirred for 5 hours at this temperature. The white slurry is cooled to room temperature, filtered through celite and the filtrate concentrated by rotary evaporation in vacuo. After distilling the excess 1,2,2,6,6-pentamethylpiperidine-4-ol in a Kugelrohr tube at 160 ° C./0.08 mbar, 7.52 g (43% o) of the compound (103) is obtained,

  melting point 73-76 ° C (Table 2).

  By analogy is obtained in Example 3 the compound (104) and the compound

  (105) (Table 2) using instead of 2,2-bis (3-cyclohexyl-4-

  hydroxyphenyl) propane 2,2-bis (3-sec-butyl-4-hydroxyphenyl) propane and 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane. Example 4 Preparation of Oligomeric Compound (106) (Table 2) a) In a 7.61 g (20.0 mmol, 1.0 equivalent) nitrogen-stirred suspension of 4,4'-cyclohexylidenebis (2-tert-butylphenol) and 0.10 g (0.80 mmol) of 4-dimethylaminopyridine in 40 ml of toluene, 2.60 ml (4.12 g, 30.0 mmol) are added dropwise at 50.degree. 1.5 equivalents) of phosphorus trichloride. The reaction mixture is then heated to 105 ° C. in one hour and stirred for 1.5 hours at this temperature. After stopping the evolution of hydrochloric gas, stirring is continued at 105 ° C. for 30 minutes under a slight stream of nitrogen. The solution obtained is diluted with 20 ml of toluene and the trichloride is distilled off.

  excess phosphorus together with about 20 ml of toluene.

  b) In a nitrogen-stirred suspension of 9.42 g (60.0 mmol, 3.0 equivalents) of 2,2,6,6-tetramethylpiperidin-4-ol and 10.12 g (100 mmol; 5.0 equivalents) of triethylamine in 100 ml of toluene, the solution described above (Example 4a) was added dropwise in 10 minutes at room temperature. The slurry is then heated to 105 ° C. and stirred for 5 hours at this temperature. The reaction mixture is cooled to room temperature, filtered through celite, and the filtrate is concentrated by rotary evaporation in vacuo. Drying the residue under high vacuum gives 12.26 g

  (70%) of the oligomeric compound (106), mp 69-78 ° C (Table 2).

  Example 5 Preparation of the Oligomeric Compound (107) (Table 2) In a similar manner to Example 4, 16.92 g (89%) of the oligomeric compound (107) are obtained, mp 53-58 ° C. (Table 2). ) using 10.28 g (60.0 mmol, 3.0 equivalents) of 1,2,2,6,6-pentamethylpiperidin-4-ol in place of 2,2,6,6-tetramethylpiperidine-4- ol. Example 6 Preparation of Oligomeric Compound (108) (Table 2) a) In a suspension stirred under a nitrogen atmosphere of 7.61 g (20.0 mmol, 1.0 equivalent) of 4,4'-cyclohexylidene-bis ( 2-tert-butylphenol) and 0.26 g (0.80 mmol) of tetrabutylammonium bromide in 40 ml of toluene are added dropwise at 50 ° C. 2.10 ml (3.30 g, 24.0 mmol; 1.2 equivalents) of phosphorus trichloride. Then heated to 105 C in one hour and stirred for 1.5 hours at this temperature. After stopping the evolution of hydrochloric acid, stirring is continued at 105 ° C. for 30 minutes under a gentle stream of nitrogen, the resulting solution is diluted with 20 ml of toluene and the excess phosphorus trichloride is distilled off.

  same time as about 20 ml of toluene.

  b) In a nitrogen-stirred suspension of 4.80 g (28.0 mmol, 1.4 equivalents) 1,2,2,6,6-pentamethylpiperidin-4-ol and 10.12 g (100 ml). 5.0 mmol) of triethylamine in 100 ml of toluene, the solution described above (Example 6a) is added dropwise over 10 minutes at room temperature. The slurry is then heated to 105 ° C. and stirred for 5 hours at this temperature. The reaction mixture is cooled to room temperature, filtered through celite, and the filtrate is concentrated by rotary evaporation in vacuo. Drying the residue under high vacuum gives 12.2 g

  (95%) of the oligomeric compound (108), mp 95-115 ° C (Table 2).

  N o t OOHH HO úV't, | T'Oi 9E'OL | O HD /, O HHO

8S'ZT L-IS 'HO, HO' I OH OH

HO- Od-O 0-d O N-OOH

OO'S SZ'0I 89'OLHOO H

Hoc? H

m. h ..-

HO HO

Lg'LZI Z; -s'1 o869 '- HO H | 0

9Z'ú001 68'9H - '. 0 ...... -

9VS'5 ú0'0I 68'69'HO OH

HO 'HO

  (wdd) (noll / nole) t4 (NIdGD (% 6) ## EQU1 ## Table 2: Oligomeric compounds n compound Mn Mw / Mn T (OC) OH3

H3C I C, 3

  % 3c-% cH 103 _I_ 1080a) 1.90a) 73-76 104 _I - 1285a) 1.96a) 45 104 25a 779a4a) O-P (CH3) 2C CH3xCH2CH (CH3) 2 n _CH3

H3C ICH '

_go -774a) 2,50a) oil

C 0

 H3-12CHDC) "CH <M)

HCC CHn n H

H3C 1CH3

  106 O1 1826b) 1.30b) 69-78 3CH3 H3C C3 n O- \ C

H3C. \

  Table 2: Oligomeric compounds (continued) n Mn Mw / Mn TF compound (C)

-% '%

M3C 'c'3

H3C H

  ## EQU1 ## n Mn = number average molecular weight Mw = weight average molecular weight a) determination by GPC (gel permeation chromatography) b) determination by MALDI ("MatrixAssisted Laser Desorption Ionisation") Example 7: Stabilization of polypropylene during a multiple extrusion 1.3 kg of polypropylene powder (Profax 6501) are mixed,

  stabilized with 0.025% Irganox 1076 (3- [3,5-di-tert-butyl-4hydroxy-

  n-octadecyl phenyl] propionate), (having a melt index of 3.2 (measured at

  230 C and 2.16 kg), with 0.05% Irganox 1010 (tetrakis [3- (3,5-ditert-butyl)

  4-hydroxyphenyl) propionate] pentaerythrityl), 0.05% calcium stearate, 0.03% dihydrotalcite [DHT 4A, Kyowa Chemical Industry Co., Ltd., Mg4.5Al2 (OH) 13CO3 · 3.5H2O] and 0.05% of the compound of Table 2. This mixture is extruded in an extruder having a sheath diameter of 20 mm and a length of 400 mm, at 100 rpm, adjusting the three heating zones at the following temperatures: 260, 270, 280 C. The extrusion product is passed through a water bath for cooling, and then granulated. This granulate is extruded from

  repeatedly. The melt index (at 230 ° C. with 2.16 kg) is measured after 3 extrusions.

  A significant increase in the melt index represents a strong degradation of the chains, thus a bad stabilization. The results are gathered in the

table 3.

Table 3

  Table 2 composite melt index after 3 extrusions

- 20.0

103 5.2

104 5.3

5.2

  Example 8 Stabilization of polyethylene during shaping 100 parts of polyethylene powder (Lupolen 5260 Z) are mixed

  with 0.05 parts of Irganox 1010 (tetrakis [3- (3,5-di-tert-butyl-4hydroxy)

  pentaerythrityl phenyl) propionate) and 0.1 part of stabilizer from Table 1 or 2 and kneaded in a Brabender plastograph at 220 ° C and 50 rpm. During this time, the kneading resistance is continuously measured in the form of the rotational torque. During mixing, the polymer begins to crosslink, after prolonged holding at a constant value, which can be determined by the rapid increase in torque. Table 4 shows the time needed to achieve a significant increase in torque as a measure of stabilizing activity. The stabilizing activity is all the better as this time is long. Table 4 composed of Table 1 and Table 2 required time for increasing torque (minutes)

- 5.0

101 15.5

102 16.0

106 15.0

107 17.0

Claims (20)

  1. Monomeric Compounds of Formula I and Oligomeric Compounds of Formula H3C C'3RR 3C CH 3 Ri-N X-P-OA-PL <-4] CH CH HI3C CH3 2A R2 H3C2C R3 R3 R H3CICH3 g4 CH - Rl H f - T-CH 3 N R 1 X O0 O-P (1) s - n A R 2   Wherein R1 and R2 independently of one another are hydrogen, C1-C25 alkyl, C2-C24 alkenyl, unsubstituted C5-C8 cycloalkyl or   substituted with C1-C4 alkyl; phenyl unsubstituted or substituted by C1-C4alkyl   C4; C 1 -C 8 cycloalkenyl unsubstituted or substituted with C 1 -C 4 alkyl; or C 7 -C 9 phenylalkyl, R 3 represents a hydrogen atom or a methyl residue, R 4 represents a hydrogen atom or a C 1 -C 8 alkyl residue, O, OH, NO, -CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 1 -C 8 acyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl ring by C 1 -C 4 alkyl; R 5   A represents an oxygen or sulfur atom or the remainder -C - I R6 II He Il He CH 2 CH 2 -CH) m -O-Y-O-C-C C O- (CHC 2)   X represents an oxygen atom or / N-R7, Y and Z represent, independently of one another, a C 2 -C 8 alkylene radical, C 4 -C 8 alkylene interrupted by oxygen, sulfur or N-Rs; C 4 -C 8 alkenylene or phenylethylene, R 5 and R 6 independently of one another represent a hydrogen atom or a CF 3, C 1 -C 12 alkyl or phenyl residue, or R 5 and R 6 together with the carbon to which they are bonded a C5-C12 cycloalkylidene ring unsubstituted or substituted by C1-C4 alkyl; with the proviso that when R5 and R6 together represent hydrogen, R4 is different from hydrogen; and with the proviso that when R 1, R 2 and R 2 are simultaneously hydrogen and R 5 and R 6 are at the same time methyl, R 4 is other than hydrogen; R7 represents a hydrogen atom, a C1-C8 alkyl residue or a radical of formula III C <N-R4 (1H); H3C CH3   R8 represents a hydrogen atom or a C1-C8 alkyl residue, m is an integer of 2 to 8, and n represents a number from 2 to 25.   2. Compounds according to claim 1, in which R1 and R2 represent, independently of one another, a hydrogen atom or a C1-C18 alkyl, C2-C15 alkenyl, C5-C8 cycloalkyl or non-phenyl radical. substituted or substituted with C1-C4 alkyl; C 5 -C 8 cycloalkenyl or C 7 -C 6 phenylalkyl, R 4 represents a hydrogen atom or a C 1 -C 4 alkyl, OH, -CH 2 CN, C 4 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, allyl, propargyl, acetyl group; or C 7 -C 9 phenylalkyl; R 5   A represents an oxygen atom, a residue -C- I O 0 0 0 He He He   CH2 CH2-C-O-Y-O-C-CH 2 CH 2 - (CH 2) -O-OC-Z-C-O- (CH 2) -   X represents an oxygen atom or N-R7, Y and Z represent, independently of each other, a C2-C12 alkylene radical, C4-C12 alkylene interrupted by oxygen or / N-Rs; C 4 -C 8 alkenylene or phenylethylene, R 5 and R 6 independently of one another represent a hydrogen atom or a CF 3, C 1 -C 8 alkyl or phenyl radical, or R 5 and R 6 together with the carbon to which they are attached a C5-C8 cycloalkylidene ring; R7 represents a hydrogen atom or a C1-C8 alkyl residue, R8 represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer of 2 to 6, and n represents a number from 2 to 15.   3. Compounds according to claim 1, in which R1 and R2 represent, independently of one another, a hydrogen atom or a C1-C8 alkyl residue, cyclohexyl or phenyl.   4. Compounds according to claim 1, in which R4 represents a hydrogen atom or a C1-C4 alkyl, C4-C16 alkoxy or cycloalkoxy group.   C5-C8, allyl, propargyl, acetyl or benzyl.   5. Compounds according to claim 1, in which R1 and R2 represent, independently of one another, a hydrogen atom or a C1-C12 alkyl, C2-C12 alkenyl, C5-C8 cycloalkyl or phenyl radical. benzyl, R4 represents a hydrogen atom or a C1-C4 alkyl, C4-C16 alkoxy, C5-C8 cycloalkoxy, allyl, propargyl, acetyl or benzyl; R5 O O   A represents a residue -C-, CCH2COYOCCHCH2- or R6 O O Il He - (CH2) m-O-C-Z-C-O- (CH2) m-   X represents an oxygen atom or / N-R7, Y and Z represent, independently of each other, a C2-C8 alkylene radical, C4-C12 alkylene interrupted by oxygen; or C4-C8 alkenylene, R5 and R6 independently of one another are hydrogen, C1-C8 alkyl or phenyl, or R5 and R6 together with the carbon atom to which they are a C5-C8 cycloalkylidene ring is attached; R7 represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer of 2 to 6, and n represents a number from 2 to 10.   Compounds according to claim 1, wherein R 1 and R 2 independently of one another represent a hydrogen atom or a C 1 -C 8 alkyl, cyclohexyl, phenyl or benzyl radical, R 4 represents a hydrogen atom or a C1-C4 alkyl, C6-C12 alkoxy, acetyl or benzyl radical; R O O   R5 olo A represents a residue -C-, or -CH2CH2-CO-YOC-CH2CH2-, R6 X represents an oxygen atom, Y represents a C2-C8 alkylene radical or a C4-C12 alkylene radical interrupted by oxygen, R5 and R6 represent, independently of one another, a hydrogen atom or a C1-C8 alkyl residue, or else R5 and R6 together with the carbon atom to which they are bonded form a cycloalkylidene ring in the form of C5-C8; and n represents a number from 2 to 10.   Compounds according to claim 1, wherein R1 represents a hydrogen atom, R2 represents a hydrogen atom or a C1-C4 alkyl or cyclohexyl residue, R3 is a hydrogen atom, R4 represents an atom of hydrogen or a C 1 -C 4 alkyl residue, R 5 A represents a -C- residue, R 6 X represents an oxygen atom, R 5 and R 6 represent, independently of each other, a hydrogen atom or a C 1 -C 4 alkyl radical; C1-C4, or R5 and R6 together with the carbon atom to which they are attached form a cyclohexylidene ring; and n represents a number from 2 to 10.   8. Process for preparing the oligomeric compounds of formula II according to claim 1, characterized in that a bisphenol of formula VI or a mixture of bisphenols of formula VI R1 R1 is first reacted. HO <OH I I (VI) R2 A R2 R3 A-R3   wherein the generic symbols have the definition given in claim 1, with phosphorus trichloride to give a compound of formula VII Cl R R, Cl P 'O-P CI Cl I ci # (VII) R3 R3   in which the generic symbols have the definition given in claim 1; and then the compound of formula VII is reacted with an HALS compound of formula V or a mixture of HALS compounds of formula V CH3 NR, (m) CH3 wherein the generic symbols are as defined in claim 1 . 9. Oligomeric products obtainable by reaction of a bisphenol of formula VI or a mixture of bisphenols of formula VI with phosphorus trichloride and an HALS compound of formula V or a mixture of HALS compounds of formula V R1 Ri CH3 HO <OH (VI) HX -R (V) R2 A R2 C j R3 R3   the generic symbols having the meaning given in claim 1. A composition containing (a) an organic material exposed to degradation due to oxidation, heat or light and (b) at least one compound of formula I or II according to claim 1, or at least one   oligomeric product according to claim 9.   11. Composition according to claim 10, containing other additives, in more components (a) and (b).   12. A composition according to claim 11, containing as other additives phenolic antioxidants, light-stabilizing agents and / or shaping stabilizers.   13. Composition according to claim 11, containing as other additive   at least one benzofuran-2-one compound.   14. Composition according to claim 10, containing as constituent   (a) natural, semi-synthetic or synthetic polymers.   15. Composition according to claim 10, containing as constituent   (a) thermoplastic polymers.   16. Composition according to claim 10, containing as constituent (a) a polyolefin.   17. Composition according to claim 10, containing as constituent   (a) polyethylene or polypropylene.   18. Use of the compounds having the formulas I and II defined in claim 1 and use of the oligomeric products defined in claim 9 as stabilizers of organic materials against degradation due to oxidation, heat or light.   19. The use according to claim 18 as stabilizers for   form (heat stabilizers) in thermoplastic polymers.   20. Process for stabilizing an organic material against degradation due to oxidation, heat or light, characterized in that it is incorporated in this material or in that it is applied to this material at minus a compound having the formula I or II defined in claim 1 or at least one product   oligomer according to claim 9.