BE1009490A5 - BISPHENYLPHOSPHITES COMPOUNDS STABILIZERS IN THE LIGHT TYPE hindered amine MONOMERS AND USE AS STABILIZERS OLIGOMERS. - Google Patents

Abstract

Novel monomeric compounds of formula I and novel oligomeric compounds of formula II are described in which the generic symbols have the definition given in claim 1, as organic matter stabilizers against degradation due to oxidation, heat or light .

Description

       

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  Bisphenylphosphites of light stabilizing compounds of the hindered amine type monomers and oligomers usable as stabilizers
The present invention relates to novel bisphenylphosphites of HALS (Hindered Amine Light Stabilizer = light stabilizer of the hindered amine type) monomers and oligomers, compositions containing an organic material, preferably a polymer, and the new bisphenylphosphites of HALS monomers and oligomers, as well as their application for the stabilization of organic matter against degradation due to oxidation, heat or light.



   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. Gâchter / H. Müller (Ed.), Plastics Additives Handbook, 3rd edition, p. 47, Hanser, Munich, 1990, and in patent document EP-A-356,688.



   Hindered amines, including in particular compounds containing 2,2, 6, 6-tetramethylpiperidyl groups, are preferably used as light stabilizers (Hindered Amine Light Stabilizers; HALS).



   Phosphites having HALS-like structural elements are described for example by T. König 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 FRA-2,380,290.



   There is also a need for active stabilizers for organic materials sensitive to degradation due to oxidation, heat and / or light.



   We have now 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 shaping stabilizers for synthetic polymers must be emphasized.



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

  <Desc / Clms Page number 2>

 
 EMI2.1
 in which R 1 and R 2 represent, independently of each other, a hydrogen atom or a C 1 -C 25 alkyl, C 2 -C 24 alkenyl, C 5 -C 8 cycloalkyl unsubstituted or substituted by C 1 -C 4 alkyl; phenyl unsubstituted or substituted by C1-C4 alkyl; C5-C8 cycloalkenyl unsubstituted or substituted by C1-C4 alkyl;

   or C7-C9 phenylalkyl, R3 represents a hydrogen atom or a methyl residue, R4 represents a hydrogen atom or a C1-C8 alkyl residue,, OH, NO,
 EMI2.2
 - CHCN, C1-Clg alkoxy, Cs-Ci cycloalkoxy, Cg-C alkenyl, C3-C6 alkynyl, C1-Cg acyl, C1-C6 phenylalkyl unsubstituted or substituted on the phenyl ring by alkyl Ci-C4;

   Ru
 EMI2.3
 A represents an oxygen or sulfur atom or the remainder-C-, R6 0 0 0 0 Il il il il - CH, CH, -C-0-Y-0-C-CH, CH, - or- ( CH,) -0-CZC-0- (CH) \ X represents an oxygen atom or NR

  <Desc / Clms Page number 3>

 
 EMI3.1
 Y and Z represent, independently of one another, a C-Cg alkylene residue, "C-Cg alkylene, interrupted by oxygen, sulfur or NR; Qt-Cg alkenylene or phenylethylene, Rs and R6 independently of one another represent a hydrogen atom or a residue CF3, C1-C12 alkyl or phenyl, or else Rg and R6 form together with the carbon atom to which they are linked a C5- cycloalkylidene ring C12 unsubstituted or substituted by C1-C4 alkyl;

   provided that when R5 and R represent hydrogen at the same time, R4 is different from hydrogen; and provided that when Ri, R2 and R2 are simultaneously hydrogen and R; and R represent at the same time methyl, R4 is different from hydrogen; R7 represents a hydrogen atom, a Ci-cog alkyl residue or a residue of formula III
 EMI3.2
 R8 represents a hydrogen atom or a C1-C8 alkyl residue, m is an integer from 2 to 8, and n represents a number from 2 to 25.



   An alkyl residue having up to 25 carbon atoms means a linear or branched residue such as, for example, a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl residue , n-pentyl, isopentyl, 1methylpentyle, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyle, 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 R1, R2 and R4 is for example C1-C4 alkyl, in particular C1-C12 alkyl, for example C1-C8 alkyl. A particularly preferred meaning of R1 and R2 is methyl and tert-butyl. A particularly preferred meaning of R2 is tert-butyl.



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

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 isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. An alkenyl residue of 3 to 18, in particular 3 to 12 carbon atoms, is preferred.



   A cycloalkyl radical in CC, in particular cycloalkyl in C-Cg, unsubstituted or substituted by alkyl in CI-C4, which preferably contains 1 to 3, in particular 1 or 2 linear or branched alkyl radicals, means for example a cyclopentyl residue , methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. Preference is given to a C5-C8 cycloalkyl radical, in particular cyclohexyl.



   A phenyl residue substituted by C1-C4 alkyl, which preferably contains 1 to 3, in particular 1 or 2 alkyl groups, means for example an o-, m- or pmethylphenyl, 2,3-dimethylphenyl, 2,4- dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-
 EMI4.1
 ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.



  A C 1 -C 6 cycloalkenyl radical, 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, methylcyclopentenyl, dimethylcyclopentenyl, cyclohexenyl radical , methylcyclohexenyl, dimethylcyclohexenyl, trimethylcyclohexenyl, tert-butylcyclohexenyl, cycloheptenyl or cyclooctenyl. The cyclohexenyl residue is preferred.



   A CC phenylalkyl radical which is unsubstituted or substituted on the phenyl radical by C1-C4 alkyl, which preferably contains 1 to 3, in particular 1 or 2 linear or branched alkyl radicals, signifies for example a benzyl, α-methylbenzyl radical, a, a-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2, 6-dimethylbenzyl or 4tert-butylbenzyl. The benzyl residue is preferred.



   An alkoxy residue having up to 18 carbon atoms means a linear or branched residue such as, for example, a methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. An alkoxy residue of 6 to 12 carbon atoms is preferred.



   A cycloalkoxy residue of 5 to 12 carbon atoms signifies, for example, a cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclodecyloxy or cyclododecyloxy residue. One of the preferred meanings of R4 is a Cs-Cg cycloalkoxy residue. Cyclopentyloxy and cyclohexyloxy residues are particularly preferred.

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   An alkynyl residue of 3 to 6 carbon atoms signifies a linear or branched residue such as, for example, a propynyl (propargyl) (-CH2-C # CH), 2butynyl or 3-butynyl residue.
 EMI5.1
 



  An acyl residue of 1 to 8 carbon atoms means, for example, a formyl, acetyl, propionyl, butyryl, pentanole, hexanoyl, heptanoyl, octanoyl, benzoyl, acryloyl or crotonyl residue. Preferred are C1-C8 alkanoyl, C alkenoyl; -Cg or benzoyl, in particular acetyl.



  A C-Cg 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, dimethylcyclopentylidene, cyclohexylidene residue, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Cyclohexylidene and tert-butylcyclohexylidene residues are preferred.



   A C1-alkylene residue means a linear or branched residue such as, for example, an ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene residue. A C 1 -C alkylene residue, for example C 2 -C 6 alkylene, is preferred.



   A C 1 -C 6 alkylene residue interrupted by oxygen, sulfur or
 EMI5.2
 \ can be interrupted once or more and means for example -CH2CH2-0-CH2CH2 -, - CH2CH2-S-CH2CH2 -, - CH2CH2-NH-CH2CH2-, - CH2CH2-N (CH3) -CH2CH2 -, - CH2CH2- 0-CH2CH2-0-CH2CH2-, - CH2CH2- (O-CH2CH2-) 20-CH2CH2 -, - CH2CH2- (O-CH2CH2-) 30-CH2CH2- or -CH2CH2- (O-CH2CH2-) 4O-CH2CH2- .



   When Y or Z is a C-C8 alkenylene residue, it is for example the 2-butenylene-1,4 residue.
 EMI5.3
 



  The phenylethylene residue signifies -CH (C6Hs) CH2-.



  Preferred are the monomeric compounds of formula 1 and the oligomeric compounds of formula (II), in which R1 and R2 independently of one another represent a hydrogen atom or a C1-C18 alkyl, C2-alkenyl residue. C18, C5-C8 cycloalkyl, phenyl unsubstituted or substituted by C1-C4 alkyl;

   C5-C8 cycloalkenyl or C-C phenylalkyl, Rt represents a hydrogen atom or a C1-C4 alkyl residue, OH, -CH2CN,

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 EMI6.1
 C-C6 alkoxy, C5-C12 cycloalkoxy, allyl, propargyl, acetyl or phenylalkyl
 EMI6.2
 enC-C 1 1 A represents an oxygen atom, a residue-C-, 1 R6 0 0 0 0 Il Il Il Il - CH, CH, -C-0-Y-0-C-CH, CH, - or- (CH2) mOCZCO- (CH2) m-, \ X represents an oxygen atom or nose
 EMI6.3
 Y and Z represent, independently of one another, a C 2 -C 12 alkylene radical, C 4 -C 12 alkylene interrupted by oxygen or / N-;

   C 1 -C 6 alkenylene or phenylethylene, Rs and R6 independently of one another represent a hydrogen atom or a CF3 residue, C 1 -C 6 alkyl or phenyl, or else Rs and R6 form together with the atom of carbon to which they are linked a C5-C8 cycloalkylidene ring; R7 represents a hydrogen atom or a C1-C8 alkyl residue, Rg represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer from 2 to 6, and n represents a number from 2 to 15.



   Preference is also given to the monomeric compounds of formula I and the oligomeric compounds of formula II in which RI and R2 independently of one another represent a hydrogen atom or a C1-C8 alkyl, cyclohexyl or phenyl residue.



   Preferred are also the monomeric compounds of formula 1 and the oligomeric compounds of formula II in which Rt represents a hydrogen atom or a C 1 -C 4 alkyl, C 4 -C 6 alkoxy, C 1 -C 6 cycloalkoxy, allyl, propargyl, acetyl where benzyl.



   Particularly preferred compounds are the monomeric compounds of formula I and the oligomeric compounds of formula II in which RI and R2 independently of one another represent a hydrogen atom or a C1-C12 alkyl, C2-alkenyl residue C12, Cg-Cg cycloalkyl, phenyl or benzyl, Rt represents a hydrogen atom or a C1-C4 alkyl, C4-C16 alkoxy, C5-C8 cycloalkoxy, allyl, propargyl, acetyl or benzyl;

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 EMI7.1
 R <0 0 - 1 Il li A represents a remainder "C- ,.

   CH: CH-C-0-Y-0-C-CHCH- or R6 O O 0 0 - (CH-0-C-Z-C-0- (CH,) ,, -, \ X represents an oxygen atom or
 EMI7.2
 Y and Z represent, independently of each other, a C2-C8 alkylene residue, C4-Cl2 alkylene interrupted by oxygen or C4-C8 alkenylene, Rs and R6 represent independently of each other a hydrogen atom or a C1-C8 alkyl or phenyl residue, or else Rs and R6 form, together with the carbon atom to which they are linked, a C5-C8 cycloalkylidene ring; R7 represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer from 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 RI and R2 independently of one another represent a hydrogen atom or a
 EMI7.3
 C1-C8 alkyl, cyclohexyl, phenyl or benzyl, R represents a hydrogen atom or a C1-C4 alkyl, C-C alkoxy
 EMI7.4
 acetyl or benzyl;

   Rs 0 0 1 it A represents a residue-C-, or-CHCH-C-0-Y-O-C-CHCH-, 1 R6
 EMI7.5
 X represents an oxygen atom, Y represents a C 1 -C 6 alkylene residue, CC alkylene interrupted by oxygen, R5 and R6 independently of one another represent a hydrogen atom or an alkyl residue C1-C8, or else R; and R6 together with the carbon atom to which they are bonded form a Cg-Cg cycloalkylidene ring; and n represents a number from 2 to 10.



   Compounds of especially particular interest are the monomeric compounds of formula 1 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 residue, Rg is a hydrogen atom,

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 EMI8.1
 R represents a hydrogen atom or a C 1 -C 4 alkyl residue, R.



  1 A represents a residue-C-, R6 R 6
 EMI8.2
 X represents an oxygen atom, R5 and R6 independently of one another represent a hydrogen atom or a C1-C4 alkyl residue, or else Rs and R6 form together with the carbon atom to which they are linked a cyclohexylidene ring; and n represents a number from 2 to 10.



   Particularly preferred compounds are the monomeric compounds of formula 1 in which, when R represents a hydrogen atom, R and R6 are different from hydrogen.



   The monomeric compounds of formula 1 according to the invention can be prepared in a manner known per se, by analogy to the techniques of the literature mentioned at the beginning.



   For example, and preferably, a bisphosphorodichloridite of formula IV is reacted with a HALS type compound of formula V
 EMI8.3
 where R1, R2, R3, R4, A and X have the meanings indicated, to form the monomeric compounds of formula 1 according to the invention.



   The HALS compound of formula V is used in stoichiometric amounts, preferably in a slight excess, relative to the bisphosphorodichloridite of formula IV.



   The reaction is carried out in a molten medium or in the presence of an appropriate aprotic, polar or non-polar organic solvent. This reaction takes place preferably
 EMI8.4
 in the presence of a base at temperatures between -20 ° C. and the boiling point of 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 variable quantities, ranging from

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 several times molar excess, passing 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 to a chloride which can be separated by filtration and / or washing with an appropriate aqueous or solid phase; a second solvent immiscible with water can then also be used. The products are isolated in an appropriate manner by evaporation of the organic phase and drying of the residue. The products are purified appropriately by chromatography on silica gel or by recrystallization.



   Solvents suitable 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 l acetone, ethyl methyl ketone, diethyl ketone, methylpropyl ketone or cyclohexanone), or even acetonitrile, butyl acetate, dimethylformamide, dimethyl sulfoxide or Nmethylpyrrolidone.



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



   When hydrides (for example sodium hydride, sodium borohydride or lithium aluminum hydride), alkali metals, alkali hydroxides or sodium methylate can be used as bases first the corresponding alcoholate of the HALS type compound of formula V; the reaction product which optionally forms under these conditions (for example water, methanol) is separated by distillation (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 the document de
 EMI9.1
 Patent DE-A-3 928 291 or by R. A. Bartlett et al., J. Amer. Chem. Soc. zu (19), 5699 (1987).



   The compounds of formula IV necessary for the preparation of the compounds of formula I according to the invention can be prepared in situ by analogy to the techniques of the literature mentioned above and then reacted without isolating them with the

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 HALS type compounds of formula V to form the monomeric compounds of formula I.



   The HALS type compounds of formula V are known or can be prepared by methods known per se, as described for example in patent document US-A-4,233,412.



   The oligomeric compounds of formula II according to the invention can be prepared by analogy to the monomeric compounds of formula 1 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 reacted first.
 EMI10.1
 in which R1, R2, R3 and A have the meanings indicated, with phosphorus trichloride to give a compound of formula VII
 EMI10.2
 in which Rj, R, R3, n and A have the meanings indicated; and then reacting the compound of formula VII with a HALS type compound of formula V or a mixture of HALS type compounds of formula V

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 EMI11.1
 in which Kt and X have the meanings indicated.



   The preferred reaction conditions for the second reaction step (reaction with the HALS type compound of formula V), for example the temperature, the solvent, the base or the catalyst, correspond to those already described above for the monomer compounds of formula 1 according to the invention.



   The reaction of the 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 an appropriate aprotic, polar or apolar organic solvent. This reaction preferably takes place in the presence of a base or of a transfer transfer reagent.
 EMI11.2
 phases at temperatures between 20 C and the boiling point of the solvent, in particular at temperatures between 20 C and 150 C, for example between 40 C and 120oC.



   Solvents suitable 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 l acetone, ethyl methyl ketone, diethyl ketone, methylpropyl ketone or cyclohexanone), or even acetonitrile, butyl acetate, dimethylformamide, dimethyl sulfoxide or Nmethylpyrrolidone. The preferred solvents are hydrocarbons, in particular toluene and xylene.



   The base or the 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 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. 4dimethylaminopyridine is particularly preferred.



   Suitable phase transfer reagents are for example salts

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 quaternary ammonium 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 on the molar ratio and on the concentration of the bisphenol of formula VI and of the phosphorus trichloride.



   Preferred molar ratios of bisphenols of formula VI to phosphorus trichloride are between 1: 1 and 1: 5. Particular preference is given to a molar ratio of between 1: 1 and 1: 3.



   The oligomeric compounds of formula VII are preferably not isolated.



  After the end of the reaction with the phosphorus trichloride, the excess phosphorus trichloride is separated by distillation, advantageously with part of the solvent. The solution of the oligomeric compounds of formula VII is then reacted as it is with a HALS type 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 type 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 formulas 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 adult pressure.



   Preferably used as filtration aids, for example, celite, silica gel, diatomaceous earth or aluminum silicate.



   To completely precipitate the ammonium salts, the concentrated filtration residue is preferably taken up again in a non-polar solvent such as, for example, toluene / hexane, and filtered again. The excess HALS compound of formula V is preferably removed by distillation under reduced pressure.



   The bisphenols of formula VI are known or can be prepared according to Houben-Weyl, Methoden der organischen Chemie, volume 6 / 1c, 1030.



   As already indicated, the HALS type compounds of formula V are known or can be prepared according to methods known per se, as described for example in patent document US-A-4,233,412.



   The two-step process described above preferably gives

  <Desc / Clms Page number 13>

 mixtures of oligomeric compounds of formula II.



   The present invention therefore also relates to oligomeric products obtainable by reaction of a bisphenol of formula VI or of a mixture of bisphenols of formula VI with phosphorus trichloride and a compound of HALS type of formula V or a mixture of compounds HALS type of formula V.



   The oligomeric compounds of formula II according to the invention can be linear or cyclic, as represented by formula VIII,
 EMI13.1
 in which the terminal group Ei represents, for example-PCl, a residue of formula IX or a residue of formula X
 EMI13.2
 the terminal group E2 preferably represents a chlorine atom or a residue of formula XI
 EMI13.3
 or else the terminal groups bi and b2 together form a direct bond (cyclic compounds), R and X having the meanings indicated.

  <Desc / Clms Page number 14>

 



   Preferred are the oligomeric compounds of formula VIII in which E1 represents a residue of formula IX and E represents a residue 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 the 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 as well as polymers of cycloolefins such as, for example, cyclopentene or norbomene; or 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 examples in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various methods, in particular by the following methods a) by radical route ( usually under high pressure and high temperature); b) using a catalyst, the catalyst usually containing one or more metals from groups IVb, Vb, VIb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl cashew aryl, which may have a 7t or o coordination type.

   These metal complexes can be free or fixed on a support, for example on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization, or other activators can be used, such as, for example, metal alkyl compounds, metal hydrides, metal alkyl halides, metal metal oxides or metal alkyloxanes, the metals being elements of groups la, lla and / or IIIa. The activators can for example be modified with other ester, ether, amine or silyl ether groups.

   These catalyst systems are usually called catalysts
Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocenes or SSC (Single Site Catalyst).

  <Desc / Clms Page number 15>

 



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



  3. copolymers of monoolefins and diolefins with one another or with other vinyl monomers such as, for example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with polyethylene
 EMI15.1
 low density (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene- copolymers octene, propylenebutadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene vinyl acetate copolymers and their copolymers with carbon monoxide,

   or ethylene-acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidenenorbomene; or mixtures of such copolymers with each other or with the polymers mentioned under 1., for example mixtures of polypropylene / ethylene-propylene copolymers, 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 their mixtures with other polymers such as, for example, polyamides;

   4. hydrocarbon resins (for example CS-C9) including their hydrogenated derivatives (for example adhesive resins) and mixtures of polyalkylenes and starch; 5. polystyrene, poly (p-methylstyrene), poly (a-methylstyrene); 6. copolymers of styrene or of α-methylstyrene with dienes or acrylic derivatives such as, for example, copolymers of styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-acrylate and methacrylate d 'alkyl, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; mixtures of high resilience consisting of copolymers of styrene and another polymer such as, for example, a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer;

   and styrene block copolymers such as, for example, styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

  <Desc / Clms Page number 16>

 7. graft copolymers of styrene or of α-methylstyrene such as, for example, of styrene on polybutadiene, of styrene on copolymers of polybutadiene-styrene or polybutadiene-acrylonitrile, of styrene and of acrylonitrile (or of methacrylonitrile) 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;

   styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on poly (alkyl 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 polymers ABS, MBS, ASA or AES.



  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, poly (vinyl chloride), poly (vinylidene chloride), poly (vinyl fluoride), poly (vinylidene 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 which derive from α, ss-unsaturated acids and their derivatives such as polyacrylates and polymethacrylates, poly (methyl methacrylates) modified to. high impact resistance with butyl acrylate, polyacrylamids and polyacrylonitriles.



  10. copolymers of the monomers mentioned under 9. with each other or with other unsaturated monomers such as, for example, acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acroxyitrileeacrylate alkoxyalkyl copolymers, acrylonitrile copolymers vinyl halide or acrylonitrile-alkyl methacrylate-butadiene terpolymers; 11. polymers which are derived from unsaturated alcohols and amines or from their acylated derivatives or from their acetals, such as poly (vinyl alcohol), poly (vinyl acetate), poly (vinyl stearate), poly (vinyl benzoate), poly (vinyl maleate), polyvinyl butyral, poly (allyl phthalate), polyallyl melamine, and their copolymers with the olefins mentioned in point 1.;

   12. homopolymers and copolymers of cyclic ethers, such as

  <Desc / Clms Page number 17>

   polyalkylene glycols, poly (ethylene oxide), poly (propylene oxide) or their copolymers 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. poly (phenylene oxides and sulfides) and mixtures thereof with styrene polymers or polyamides; 15. polyurethanes which are derived on the one hand from polyethers, polyesters or polybutadienes having terminal hydroxy groups and on the other hand from aliphatic or aromatic polyisocyanates, as well as their precursors;

   16. polyamides and copolyamides which are 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 an elastomer as modifying agent, for example poly (2,4, 4-trimethylhexamethyleneterephthalamide) or poly (m-phenylene-isophthalamide) ), block copolymers of the aforementioned polyamides with polyolefins, copolymers of olefins, ionomers or elastomers chemically bonded or grafted;

   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, poly (amide-imides) and polybenzimidazoles; 18. polyesters which are derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, such as poly (ethylene terephthalate), poly (butylene terephthalate), poly (terephthalate 1, 4-dimethylolcyclohexane), polyhydroxybenzoates, as well as block copolyethersesters which are derived from polyethers having terminal hydroxy groups;

   or alternatively polyesters modified with polycarbonates or MBS; 19. polycarbonates and polyestercarbonates; 20. polysulfones, polyethersulfones and polyetherketones.



  21. crosslinked polymers which are derived on the one hand from aldehydes and on the other hand from

  <Desc / Clms Page number 18>

 phenols, ureas or melamines, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins; 22. siccative and non-siccative alkyd resins; 23. unsaturated polyester resins which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyols, and of vinyl compounds as crosslinking agents, as well as their low-flammable halogenated derivatives.



  24. crosslinkable acrylic resins which are derived from substituted acrylic esters such as epoxyacrylates, 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 which derive from polyepoxides, for example from bis-glycidyl ethers or from cycloaliphatic diepoxides.



  27. natural polymers such as cellulose, natural rubber, gelatins, and their chemically modified derivatives to 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. mixtures (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, PAIHDPE, 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 oils, waxes and fats based on synthetic esters (for example phthalates, adipates, phosphates or trimellitate), as well as mixtures of synthetic esters with mineral oils in any proportions by mass, such as those which can be used for example as spinning preparations, as well as their aqueous emulsions; 30. aqueous emulsions of natural or synthetic rubbers such as, for example, natural rubber latex or latexes of carboxylated styrenebutadiene copolymers.



   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 1 or II,

  <Desc / Clms Page number 19>

 or at least one oligomer product obtainable by reaction of a bisphenol of formula VI or of a mixture of bisphenols of formula VI with phosphorus trichloride and a compound of type HALS of formula V or a mixture of compounds of type HALS of formula V.



   As regards the organic materials to be protected, they are preferably natural, semi-synthetic or preferably synthetic organic materials. Thermoplastic polymers, in particular PVC or polyolefins, especially polyethylene and polypropylene, are particularly preferred.



   Particularly noteworthy is the activity of the compounds according to the invention against degradation by heat and oxidation, especially in the event of thermal stress, such as that which occurs at the time of the forming of the thermoplastic materials. The compounds according to the invention are therefore very particularly suitable for use as shaping stabilizers.



   The monomer and oligomeric compounds of formula I and II are preferably added to the material to be stabilized in amounts of 0.01 to 10%, for example from 0.01 to 5%, preferably from 0.025 to 3%, in particular from 0.025 to 1%, relative 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 can contain other costabilizers such as, for example, the following: 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, 6-di-tertbutyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4, 6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2, 6-dinonyl-4-methylphenol, 2, 4-dimethyl- 6- (l'-methyl-1'-undécyl) phenol, le 2,

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



  1.2. alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.



  1.3. hydroquinones and alkvlée hydroquinones. for example 2,6-di-tertbutyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octadecyloxyphenol, 2 , 6-di-tert-

  <Desc / Clms Page number 20>

 butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, adipate bis (3,5-di-tert-butyl-4-hydroxyphenyl).



  1.4. tocopherols, for example a-tocopherol, ss-tocopherol, y-tocopherol, 8-tocopherol and their mixtures (vitamin E).
 EMI20.1
 



  1. 5. hydroxylated thiodiphenyl ethers, for example 2, 2'-thiobis (6-tert-butyl-4- 1. 5. thiodil2henyl ethers hy methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3methylphenol), 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-tert-butyl-4methylphenol), 2, 2'-methylenebis (6-tert-butyl-4-ethylphenol), 2, 2'-
 EMI20.2
 methylenebis (4-methyl-6- (a-methylcyclohexyl) phenol], 2, 2'-methylenebis (4-methyl-6-cyclohexylphenol), 2, 2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tertbutylphenol), 2,2'-ethylidenebis (6-tert-butyl- 4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2, 2'-methylenebis (6- (a, a-dimethylbenzyl) -4-nonylphenol] 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,

     4'-methylenebis (6-tert-butyl-2-methylphenol), 1, 1-bis (5-tert-butyl-4hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl- 5-methyl-2-hydroxy-
 EMI20.3
 benzyl) -4-methylphenol, 1, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis (5-tert-butyl-4-hydroxy Ethylene glycol -2-methylphenyl) -3-n-dodecylmercaptobutane, bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4- hydroxy-5-methylphenyl) dicyclopentadiene, bis (2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate], 1, 1- bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,

  2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1, 1, 5,5-tetra (5-tertbutyl-4-hydroxy-2-methylphenyl) pentane.



  1.7. 0- compounds. N- and S-benzylated. for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl oxide, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris (3,5- di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4) sulfide -hydroxybenzyle), isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.



  1.8. hydroxybenzylated malonates, for example 2,2-bis (3,5-di-tert-butyl-2hydroxybenzyl) dioctadecyl malonate, 2- (3-tert-butyl-4-hydroxy-5-

  <Desc / Clms Page number 21>

 dioctadecyl methylbenzyl) malonate, 2,2-bis (3,5-di-tert-butyl-4hydroxybenzyl) didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) di [4- (1, 1, 3,3-tetramethylbutyl) phenyl malonate].



  1. 9. hydroxybenzylated aromatic compounds, for example 1, 3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2, 4, 6-trimethylbenzene, 1, 4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) - 2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4hydroxybenzyl) phenol.



  1. 10. triazine compounds, for example 2, 4-bis-octylmercapto-6- (3, 5-di-
 EMI21.1
 tert-butyl-4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-ditert-butyl-4-hydroxyanilino) -1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-ditert-butyl-4-hydroxyphenoxy) -1, 3, 5-triazine, la 2, 4, 6-tris (3, 5-di-tert-butyl- 4hydroxyphenoxy) -l, 2, 3-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3, 5-tris (4-tert-butyl -3-hydroxy-2,6-dimethylbenzyl) isocyanurate, la 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxyphenylethyl) -1, 3, 5-triazine, la 1, 3, 5-tris (3,5-di-tert-butyl-4-hydroxyphenytpropionyl) hexahydro-1,3,5triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.



  1.11. benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert- dioctadecyl butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.



  1.12. acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4-hydroxyanilide of stearic acid, N- (3,5-di-tert-butyl-4hydroxyphenyl) carbylate octyl.



  1.13 esters of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol , 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N 'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7 trioxabicyclo [2. 2.2] octane.



  1. 14. esters of 6-f5-tert-butvl-4-hvdroxv-3-methvlphénvnpropionique acid with mono-or polyalcohols, for example with methanol, ethanol, octanol, octadecanol , 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,

  <Desc / Clms Page number 22>

 1, 2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7trioxabicyclo [2. 2.2] octane.



  1. 15. esters of ss- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonandiol, ethylene glycol, 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N ' bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7-trioxabicyclo [2. 2.2] octane.



  1.16. esters of 3. S-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6- hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'bis (hydroxyethyl) oxamide , 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7trioxabicyclo [2. 2.2] octane.
 EMI22.1
 



  1. 17. amides of ss- (3. 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3, 5-di-tert-butyI-4 -hydroxyphenylpropionyl) hexamethylene diamine, N, N'-di- (3, 5-di-tert-butyI-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-di- (3,5-di-tet -butyl-4-hydroxyphenylpropionyl) 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) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1, 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'- hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole , 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxy-
 EMI22.2
 phenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', S'-di -tert-amyl- 2'-hydroxyphenyl) benzotriazole, 2- (3', S'-bise a, a -dimethylbenzyl) -2'-hydroxyphenyl)

   benzotriazole, a mixture of 2- (3'-tert-butyl-2-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotnazole, of 2- (3'-

  <Desc / Clms Page number 23>

 
 EMI23.1
 tert-butyl-5'- {2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, of 2- (3'-tert-butyl- 2'-hydroxy- 5'- (2- methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2 ') -hydroxy-5'- (2octyloxycarbonylethyl) phenyl) benzotriazole, of 2- (3'-tert-butyl-5'- [2- (2- ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, of 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, 3tetramethylbutyl) -6- (benzotriazole-2-yl) phenol];

   the transesterification product of 2- [3'-tert-butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotnazole with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2- with R = 3'-tert-butyl- 4'-hydroxy-5'- (2H-benzotriazole-2-yl) phenyl.



  2. 2. 2-hydroxybenzophenones. for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2-hydroxy-4,4'-dimethoxy derivatives.



  2. 3. esters of optionally substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis- (4-tert-butylbenzoyl) resorcinol, benzoyiresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoate of 2,4-di-tertbutylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate of hexadecyl, 3,5-di octadecyl-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.



  2.4. acrylates. for example, ethyl or isooctyl &alpha; -cyano-ss, ss-diphenylacrylate, methyl a-carbomethoxycinnamate, a-cyano-ss-methyl-p-
 EMI23.2
 methyl or butyl methoxycinnamate, methyl α-carbomethoxy-pmethoxycinnamate, N- (ss-carbomethoxy-p-cyanovinyl) -2-methylindoline.



  2. 5. from nickel compounds, for example complexes of nickel with 2,2'-thiobis [4- (1, 1, 3,3-tetramethylbutyl) phenol], such as complex 1: 1 or complex 1 : 2, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutylnickel dithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5di-tert-butylbenzylphosphonic acid , like methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4methylphenylundecyl ketoxime, nickel complexes with 1-phenyl-4lauroyl-5-hydroxypyrazole, possibly with other ligands.

  <Desc / Clms Page number 24>

 



  2.6. sterically hindered amines, for example bis (2,2,6,6tetramethylpiperidyl) sebacate, bis (2,2,6,6,6-tetramethylpiperidyl succinate), bis (1,2,2,6,6) sebacate 6-pentamethylpiperidyl), bis (1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl-4hydroxybenzylmalonate), 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-4piperidyl) hexamethylenediamine and 4-tert- octylamino-2, 6-dichloro-1, 3,5triazine, nitrilotriacetate of tris (2,2, 6,6-tetramethyl-4-piperidyle), 1,2, 3,4butanetetracarboxylate 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-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 2-n-butyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) bis malonate (1,2,2,6,6-pentamethylpiperidyl), 3-n-octyl-7,7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4. 5] decane-2,4dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, succinate
 EMI24.1
 bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl), the condensation product of N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4morpholino- 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 1,2bis (3-aminopropylamino) ethane, the condensation product of 2-chloro-4,

  6di (4-n-butylamino-1, 2,2, 6, 6-pentamethylpiperidyl) -1, 3,5-triazine and 1, 2-bis (3-
 EMI24.2
 aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetramethyl-1, 3, 8triazaspiro [4. 5] decane-2, 4-dione, 3-dodecyl-1- (2, 2, 6, 6-tetramethyl-4piperidyl) pyrrolidin-2, 5-dione, 3-dodecyl-l- (1, 2, 2, 6, 6-pentamethyl-4piperidyl) 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-tert-butyloxanilide and mixtures of oxanilides disubstituted by methoxy at o and p, and by ethoxy at o and p .



  2. 8. des 2-2-hvdroxvphénvn-1. 3.5-triazine. 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) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2, 4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4, 6bis (4-methylphenyl) - 1, 3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4, 6-

  <Desc / Clms Page number 25>

 bis (2,4-imethylphenyl) -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-
 EMI25.1
 hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.



  3. Metal deactivators, for example N, N'-diphenyloxamide, Nsalicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5di-tert -butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-l, 2,4triazole, bis (benzylidene) dihydrazide of oxalic acid, oxanilide, dihydrazide of isophthalic acid, bis (phenylhydrazide) sebacic acid, N, N'diacetyldihydrazide of adipic acid, N, N'-bis-salicyloyldihydrazide of oxalic acid, 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, trioctadecyl phosphite, disteararylpentaerythritol diphosphite , tris (2,4-ditert-butylphenyl) phosphite, diisodecylpentaerythritol 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-tert-butylphenyl diphosphite) ) pentaerythritol, the tristearylsorbitol triphosphite,
 EMI25.2
 tetrakis diphosphonite (2,4-di-tert-butylphenyl)

  -4, 4'-biphenylylene, 6isooctyloxy- 2, 4, 8, 10-tetra-tert-butyl-12H-dibenzo [d, g] -l, 3, 2-dioxaphosphocine, la6-fluoro-2, 4, 8, 10-tetra-tert-butyl-12-methyldibenzo [d, g] -1, 3, 2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, ethylphosphite bis (2,4-di-tert-butyl-6-methylphenyl).



  5. Compounds which destroy peroxides, for example esters of thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate, disulfide of dioctadecyl, pentaerythritol tetrakis (ss-dodecylmercapto) 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

  <Desc / Clms Page number 26>

 Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate or tin pyrocatecholate.



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



  9. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulphate, 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
 EMI26.1
 patent documents US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A- 5216052, US-A-5 252 643, DE-A-4 316 611, DE -A-4 316 622, DE-A- 4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2- one, 5, 7-di-tert-butyl- 3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3, 3'-bis [5, 7-di-tert-butyl-3 - (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], Ia5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3 , 5-dimethylphenyl) -5, 7di-tert-butylbenzofuran-2-one, la 3- (3, 5-dimethyl-4-pivaloyloxyphenyl) -5,

     7-di-tert-butylbenzofuran-2-one.



   Costabilizers, with the exception of the benzofuranones described in point 11, are added for example at concentrations of 0.01 to 10% relative to the total mass of the material to be stabilized.



   Other preferred compositions contain, in addition to component (a) and monomer and oligomeric compounds of formulas 1 and II, still other additives, in particular phenolic antioxidants, light stabilizers and / or light stabilizers. shaping.



   Particularly preferred additives are phenolic antioxidants (list item 1), sterically hindered amines (list item 2.6), phosphites and phosphonites (list item 4) and peroxide-destroying compounds (item 5 of the list).



   Other particularly preferred additives (stabilizers) are also benzofuran-2-ones as described for example in the documents of
 EMI26.2
 Patent US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A-5,252,643, DE-A-4,316,611, DE -A-4 316 622, DE-A-4 316 876, EP-A- 0 589 839 or EP-A-0 591102.

  <Desc / Clms Page number 27>

 



   Examples of such benzofuran-2-ones are compounds of the formula
 EMI27.1
 wherein R'n 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 residue of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chloro;

   R'13 has the meaning of R'12 or R'14 or represents a residue of formula
 EMI27.2
 or-DE, where R'is 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 total 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl substituted by 1 to 3 alkyl radicals having altogether up to 18 carbon atoms; s is 0, 1 or 2;

   the substituents R'17 are, independently of one another, a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl
 EMI27.3
 substituted by 1 or 2 alkyl radicals having altogether up to 16 carbon atoms, a residue 0 Il of formula -CH4OH, -C2H4-O-CtH2i or-C2H-0-C-R'20 or form together

  <Desc / Clms Page number 28>

 
 EMI28.1
 with the nitrogen atom to which they are linked a piperidine or morpholine residue; t is a number from 1 to 18; R'20 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 residue 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 altogether up to 16 carbon atoms or benzyl; R'19 represents an alkyl residue of 1 to 18 carbon atoms; D is O -, - S -, - SO -, - SO-or-C (R'2i) 2-; the substituents R'2l represent, independently of one another, a hydrogen atom or a C1-Cl6 alkyl residue, the two residues Ri together containing 1 to 16 carbon atoms, and Ri is also a phenyl residue or a rest of formula 0 0 Il Il - (CH-C-OR ', or- (CHC-N (R' where s, R'ig and R'17 have the meanings given above;

   E is a remainder of formula
 EMI28.2
 
 EMI28.3
 in which R'n, R 'and R'14 have the meanings given above; and R \ s represents a hydrogen atom or an alkyl residue of 1 to 20 carbon atoms,
 EMI28.4
 U il cyclopentyle, cyclohexyle, chloro or a residue of formula-CH-C-OR 'or o 0. il CH-C-N (R 'where R'i6 and R'17 have the meanings given above, or
 EMI28.5
 R'15 forms with R'14 a tetramethylene residue.



  Benzofuran-2-ones are preferred in which R'I3 represents a hydrogen atom or an alkyl residue of 1 to 12 carbon atoms, cyclopentyl,, ...
 EMI28.6
 



  '-' Il cyclohexyle, chloro, or a residue of formula- (CHC-OR '0 Il - (CHC-N (R') ou-D-E, where s, R \ 6 and R ', D and E have the meanings
 EMI28.7
 given above, R'16 having in particular the meaning of a hydrogen atom

  <Desc / Clms Page number 29>

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



   Furthermore, benzofuran-2-ones are preferred in which R'n represents a phenyl or phenyl radical substituted by 1 or 2 alkyl radicals having together up to 12 carbon atoms; R'12 is a hydrogen atom; R 'is a
 EMI29.1
 hydrogen atom or an alkyl residue of 1 to 12 carbon atoms; R'ig is an atom
 EMI29.2
 U Il of hydrogen or an alkyl residue of 1 to 12 carbon atoms, - (CH-C-OR 'o 0 Il - (CHC'N (R'j or-DE; R'is is a hydrogen atom or an alkyl residue of 1 0 0 Il N with 20 carbon atoms, -CH-C-OR ', or -CHC-R' or R'i; form
 EMI29.3
 with R \ 4 a tetramethylene residue, s, R'16, R'17, D and E having the meanings given initially.



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



   We can finally put a particular emphasis on the interest of benzofuran-2-ones in which R'13 represents an alkyl residue of 1 to 4 carbon atoms or - D-E; R'12 and R 'are a hydrogen atom; and R'is represents an alkyl residue of 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D being a group -C (R'21) 2- and E a residue of formula
 EMI29.4
 where 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'll, R ', R'14 and R'15 have the meanings indicated .



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

  <Desc / Clms Page number 30>

 



   The incorporation of the monomeric and oligomeric compounds of formula 1 and II and optionally other additives into the polymeric organic material is carried out according to known methods, for example before or during shaping or by application of the compounds in solution or in dispersion on the organic polymeric material, optionally followed by evaporation of the solvent. The compounds of formulas 1 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 mass.



   It is also possible to add the monomeric and oligomeric compounds of formula 1 and II according to the invention before or during the polymerization or before the crosslinking.



   The monomeric and oligomeric compounds of formula 1 and II can be incorporated into the material to be stabilized in pure form or in form encapsulated in waxes, oils or polymers.



   It is also possible to spray the monomeric and oligomeric compounds of formulas 1 and II onto the polymer to be stabilized. They are able to dilute other additives (for example the common 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 addition by spraying during deactivation of the polymerization catalysts is particularly advantageous, the vapor used for deactivation being able for example to 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 1 and II according to the invention by spraying, optionally at the same time as other additives.



   The materials thus stabilized can be used in the most varied forms, for example in the form of sheets, fibers, strips, moldable materials, profiles or as binders for paints, adhesives or cements.



   As mentioned above, it is preferably, with regard to the organic materials to be protected, organic polymers, in particular synthetic polymers. Thermoplastics, in particular polyolefins, are protected here in a particularly advantageous manner. Above all, emphasis must be placed on the excellent activity of the compounds of formula 1 as shaping stabilizers (heat stabilizers). To this end, 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 oxidation and

  <Desc / Clms Page number 31>

 heat.

   The elastomers are to be taken from the above list of possible organic materials.



   The lubricants and hydraulic fluids to be taken into account 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" (Editions Chemie, Weinheim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch "(Editions Dr Alfred Hüthig, Heidelberg, 1974) and in" Ulmanns Enzyklopâdie der technischen Chemie ", volume 13, pages 85-94 (Editions Chemie, Weinheim, 1977).



   A preferred embodiment of the present invention is therefore the use of monomeric and oligomeric compounds of formula 1 and II and of products obtainable by reaction of a bisphenol of formula VI or of a mixture of bisphenols of formula VI with phosphorus trichloride and a HALS type compound of formula V or a mixture of HALS type compounds of formula V, for stabilizing organic matter against degradation induced by oxidation, heat or light.



   The monomeric and oligomeric compounds of formula 1 and II according to the invention are distinguished by very good hydrolysis stability and advantageous coloring properties, namely a weak coloring of the organic materials during the treatment.



   The organic materials stabilized with the compounds of the present invention are particularly well protected against degradation induced by light.



   The present invention also relates to a method for stabilizing an organic material against degradation due to oxidation, heat or light, characterized in that it is incorporated into this material or in that it is applied on this material at least one monomer or oligomer compound of formula 1 or II or a product obtainable by reaction of a bisphenol of formula VI or of 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 type compounds of formula V.



   The following examples explain the invention in more detail. Data in parts or in percentages refer to mass.



  Example 1: Preparation of the compound (101) (Table 1). a) In a suspension stirred under a nitrogen atmosphere of 15.22 g (40.0

  <Desc / Clms Page number 32>

 mmoles; 1.0 equivalent) of 4,4'-cyclohexylidene-bis (2-tert-butylphenol) and 0.20 g (1.60 mmol) of 4-dimethylaminopyridine in 46 ml of toluene, added dropwise at temperature ambient 9.10 ml (14.28 g; 104 mmol; 2.6 equivalents) of
 EMI32.1
 phosphorus trichloride. Then heated to 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 gentle stream of nitrogen. The solution obtained is diluted with 20 ml of toluene and the excess phosphorus trichloride is distilled together with approximately 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-tetramethylpiperidine-4-ol and 22.2 g (220 mmol; 5, 5 equivalents) of triethylamine in 250 ml of toluene, the solution described above (example la) is added dropwise over 10 minutes, at room temperature. The reaction mixture is then heated to 105 ° C and continued to stir for 5 hours at this temperature. The white suspension is cooled to room temperature, filtered through celite and the filtrate is concentrated on a rotary evaporator under vacuum. The residue is taken up in a mixture of hexane / toluene solvents = 1: 1 and again filtered through celite.

   The filtrate is concentrated on a rotary evaporator under vacuum and the residue is dried under high vacuum. 17.84 g (42%) of compound (101) are obtained, melting point 48-52 C (Table 1).



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



   Analogously to Example 1, starting from 23.2 g (40.0 mmol; 1.0 equivalent) of 4,4'-cyclohexylidene-bis (2-tert-butylphenyl dichlorophosphite) (example la) in 50 ml of toluene and 27.4 g (160 mmol; 4.0 equivalents) of 1, 2,2, 6,6-pentamethylpiperidine-4-ol, 23.7 g (53%) 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 suspension stirred under nitrogen atmosphere of 7.85 g (20.0 mmol; 1.0 equivalent) of 2,2-bis (3- cyclohexyl-4-hydroxyphenyl) propane and 0.20 g (1.60 mmol) of 4-dimethylaminopyridine in 15 ml of toluene, is added dropwise at 50 C 4.55 ml (7.10 g; 52 mmol; 2 , 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 a rotary evaporator under vacuum and the residue (9.14 g) is 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

  <Desc / Clms Page number 33>

 50 ml of toluene, a solution of 10.55 g (61.6 mmol; 3.1 equivalents) of 1, 2.2, 6, 6-pentamethylpiperidine- is added dropwise over 15 minutes 4-ol and 8.57 gg (84.7 mmol; 4.2 equivalents) of triethylamine in 100 ml of toluene. The reaction mixture is then heated to 105 ° C and continued to stir for 5 hours at this temperature. The white suspension is cooled to room temperature, filtered through celite and the filtrate is concentrated on a rotary evaporator under vacuum.

   After distilling 1, 2,2, 6, 6-pentamethylpiperidine-4-ol in excess
 EMI33.1
 a tube with balls at 160 C / 0.08 mbar, 7.52 g (43%) of compound (103) are obtained, melting point 73-76 C (Table 2).



   The compound (104) and the compound (105) (Table 2) are obtained by analogy with Example 3, using 2,2-bis (3-cyclohexyl-4hydroxyphenyl) propane in place of 2,2-bis ( 3-sec-butyl-4-hydroxyphenyl) propane and 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane.



  Example 4 Preparation of the oligomeric compound (106) (Table 2) a) In a stirred suspension under a nitrogen atmosphere of 7.61 g (20.0 mmol; 1.0 equivalent) of 4,4'-cyclohexylidene-bis (2-tert-butylphenol) and 0.10 g (0.80 mmol) of 4-dimethylaminopyridine in 40 ml of toluene, added dropwise
 EMI33.2
 drop at 50 C 2, 60 ml (4.12 g; 30.0 mmol; 1.5 equivalent) 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 gentle stream of nitrogen.

   The solution obtained is diluted with 20 ml of toluene and the excess phosphorus trichloride is distilled together with approximately 20 ml of toluene. b) In a suspension stirred under a nitrogen atmosphere of 9.42 g (60.0 mmol; 3.0 equivalents) of 2.2, 6, 6-tetramethylpiperidine-4-ol and 10.12 g (100 mmol; 5.0 equivalents) of triethylamine in 100 ml of toluene, the solution described above is added dropwise over 10 minutes, at room temperature (Example 4a). The thick suspension is then heated to 105 ° C. and stirring is continued for 5 hours at this temperature. The reaction mixture is cooled to room temperature, filtered through celite and the filtrate is concentrated on a rotary evaporator under vacuum.

   Drying the residue under high vacuum gives 12.26 g (70%) of the oligomeric compound (106), melting point 69-78 C (Table 2).



  Example 5: Preparation of the oligomeric compound (107) (Table 2)
Analogously to Example 4, 16.92 g (89%) of the compound are obtained
 EMI33.3
 oligomer (107), melting point 53-58 C (Table 2) using 10.28 g (60.0 mmol; 3.0 equivalents) of 1, 2. 2, 6, 6-pentamethylpiperidine-4-ol to the place of

  <Desc / Clms Page number 34>

 2,2, 6, 6-tetramethylpiperidine-4-ol.



  Example 6 Preparation of the oligomeric compound (108) (Table 2) a) In a suspension stirred under 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, we add
 EMI34.1
 drop by drop 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 gas, stirring is continued at 105 ° C. for 30 minutes under a gentle stream of nitrogen.

   The solution obtained is diluted with 20 ml of toluene and the excess phosphorus trichloride is distilled together with approximately 20 ml of toluene. b) In a suspension stirred under a nitrogen atmosphere of 4.80 g (28.0 mmol; 1.4 equivalent) of 1, 2.2, 6, 6-pentamethylpiperidine-4-ol and 10.12 g (100 mmol; 5.0 equivalents) of triethylamine in 100 ml of toluene, the solution described above is added dropwise over 10 minutes, at room temperature (Example 6a). The thick suspension is then heated to 105 ° C. and stirring is continued for 5 hours at this temperature. The reaction mixture is cooled to room temperature, filtered through celite and the filtrate is concentrated on a rotary evaporator under vacuum.

   Drying the residue under high vacuum gives 12.2 g (95%) of the oligomeric compound (108), melting point 95-115 C (Table 2).

  <Desc / Clms Page number 35>

 
 EMI35.1
 5 MM
 EMI35.2
 
 <tb>
 <tb> n <SEP> compound <SEP> TF <SEP> C <SEP> C (%), <SEP> H <SEP> (%), <SEP> N (%) <SEP> 31P-RMN
 <tb> (CDCl3)
 <tb> (calculated / found) <SEP> (ppm)
 <tb> 101 <SEP> # <SEP> 48-52 <SEP> 69.89 <SEP> 10.03 <SEP> 5.26 <SEP> 127.37
 <tb> 69.38 <SEP> 10.00 <SEP> 4.81
 <tb> 102 <SEP> # <SEP> 51-57 <SEP> 70.68 <SEP> 10.25 <SEP> 5.00 <SEP> 128.38
 <tb> 70.36 <SEP> 10.15 <SEP> 4.43
 <tb>
 

  <Desc / Clms Page number 36>

 
 EMI36.1
 Table 2:

   Oligomeric compounds
 EMI36.2
 
 <tb>
 <tb> T
 <tb> n <SEP> compose <SEP> Mn <SEP> Mw / Mn <SEP>
 <tb> (OC)
 <tb> 103 <SEP> # <SEP> 1080a) <SEP> 1.90a) <SEP> 73-76
 <tb> n
 <tb> 104 <SEP> # <SEP> 1285a) <SEP> 1.96a) <SEP> 45
 <tb> n
 <tb> 105 <SEP> # <SEP> 774a) <SEP> 2.50a) <SEP> oil
 <tb> H
 <tb> H, <SEP> C <SEP>! <SEP> CH.
 <tb>



  106 <SEP> # <SEP> 1826b) <SEP> 1.30b) <SEP> 69-78
 <tb>
 

  <Desc / Clms Page number 37>

 
 EMI37.1
 Table 2: Oligomeric compounds (continued) 1.
 EMI37.2
 
 <tb>
 <tb> n <SEP> compound <SEP> Mn <SEP> Mw / Mn <SEP> TF
 <tb> (C)
 <tb> 107 <SEP> # <SEP> 1752b) <SEP> 1.30b) <SEP> 53-58
 <tb> 108 <SEP> 2065b) <SEP> 1.30b) <SEP> 95-115
 <tb>
 
 EMI37.3
 Mn = number average molecular weight Mw = weight average molecular weight a) determination by GPC (gel permeation chromatography) b) determination by MALDI ("Matrix Assisted Laser Desorption Ionization") Example 7:

   Polypropylene stabilization during a multiple extrusion 1.3 kg of polypropylene powder (Profax 6501), pre-stabilized with 0.025% Irganox 1076 (3- [3,5-di-tert-butyl-4-) is mixed n-octadecyl hydroxyphenyl] propionate), (having a melt index of 3.2 (measured at 230 C and with 2.16 kg), with 0.05% of lrganox 1010 (tetrakis [3- (3, 5 -di-tert-butyl- 4-hydroxyphenyl) pentaerythrityl propionate), 0.05% calcium stearate, 0.03% dihydrotalcite [DHT 4A, Kyowa Chemical Industry Co., Ltd, g4, 5Al2 (OH) 13C033 0.5 H 2 O] and 0.05% of the compound in Table 2. This mixture is extruded in an extruder having a barrel diameter of 20 mm and a length of 400 mm, at 100 revolutions per minute, adjusting the three heating zones at the following temperatures: 260, 270, 280 C.

   We pass the extrusion product

  <Desc / Clms Page number 38>

 in a water bath to cool it, then it is granulated. This granule is repeatedly extruded. The melt index is measured (at 2300C with 2.16 kg) after 3 extrusions.



  A significant increase in the melting index represents a strong degradation of the chains, therefore poor stabilization. The results are collated in Table 3.



   Table 3
 EMI38.1
 
 <tb>
 <tb> compound <SEP> from <SEP> array <SEP> 2 <SEP> index <SEP> from <SEP> fusion <SEP> after <SEP> 3 <SEP> extrusions
 <tb> - <SEP> 20, <SEP> 0
 <tb> 103 <SEP> 5.2
 <tb> 104 <SEP> 5.3
 <tb> 105 <SEP> 5, <SEP> 2
 <tb>
 EXAMPLE 8 Stabilization of Polyethylene During Shaping
100 parts of polyethylene powder (Lupolen 5260 Z) are mixed with 0.05 parts of Irganox 1010 (pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)) and 0.1 part of stabilizer from table 1 or 2 and kneaded in a Brabender plastograph at 220 C and 50 revolutions per minute. During this time, the kneading resistance is continuously measured in the form of the torque.

   During mixing, the polymer begins to crosslink, after prolonged holding at a constant value, which can be determined by means of the rapid increase in the torque. Table 4 shows the time required 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
 EMI38.2
 
 <tb>
 <tb> compound <SEP> from <SEP> array <SEP> 1 <SEP> and <SEP> from <SEP> array <SEP> 2 <SEP> time <SEP> required <SEP> for <SEP> the increase <SEP> from
 <tb> couple <SEP> from <SEP> rotation <SEP> (minutes)
 <tb> - <SEP> 5, <SEP> 0
 <tb> 101 <SEP> 15.5
 <tb> 102 <SEP> 16.0
 <tb> 106 <SEP> 15.0
 <tb> 107 <SEP> 17, <SEP> 0
 <tb>



    

Claims (1)

 CLAIMS 1. Monomeric compounds of formula I and oligomeric compounds of formula II  EMI39.1  in which R 1 and R 2 represent, independently of each other, a hydrogen atom or a C 1 -C 25 alkyl residue, C 2 -C 24 alkenyl, C 5 -C 8 cycloalkyl unsubstituted or substituted by C 1 -C alkyl; phenyl unsubstituted or substituted by C1-C4 alkyl; Cs-Cg cycloalkenyl unsubstituted or substituted by C1-C4 alkyl;  or phenylalkyl in Cr-4, R3 represents a hydrogen atom or a methyl residue, R4 represents a hydrogen atom or a C1-C8 alkyl residue,, OH, NO, - CH2CN, C1-C6 alkoxy, cycloalkoxy C5-C12, C3-C6 alkenyl, C3-C6 alkynyl, C1-C8 acyl, C7-C9 phenylalkyl unsubstituted or substituted on the phenyl ring by C1-C4 alkyl;    <Desc / Clms Page number 40>    EMI40.1  R5 A represents an oxygen or sulfur atom or the remainder C P6 OOOO oo o 0 0 0 0 Il Il il il - CH, CH, -C-0-Y-0-C-CH, CH- or- ( CH-0-CZC-0- (CH- "X represents an oxygen atom or N - R7 '  EMI40.2  Y and Z represent, independently of one another, a C 1 -C 6 alkylene, C 4 -C 18 alkylene residue interrupted by oxygen, sulfur or N-Ra; C4-CS alkenylene or phenylethylene, RS and R6 independently of one another represent a hydrogen atom or a CF3 residue, C1-C12 alkyl or phenyl, or else R5 and R6 form together with the atom of carbon to which they are linked a C5-C12 cycloalkylidene ring which is unsubstituted or substituted by C1-C4 alkyl;  provided that when R5 and R6 represent hydrogen at the same time, R4 is different from hydrogen; and provided that when R1, R2 and R3 are simultaneously hydrogen and R5 and R6 represent methyl at the same time, R4 is different from hydrogen; R7 represents a hydrogen atom, a C1-C8 alkyl residue or a residue of formula  EMI40.3   Rg represents a hydrogen atom or a C1-Cg alkyl residue, m is an integer from 2 to 8, and n represents a number from 2 to 25; provided that in the monomeric compound of formula I, R5 and R6 are neither hydrogen nor C1-C12 alkyl.  2. Compounds according to claim 1. in which RI and R2 independently of one another represent a hydrogen atom or a C1-C18 alkyl, C-Cig alkenyl, C5-C8 cycloalkyl, non-phenyl substituted or substituted by alkyl in  EMI40.4  C 1- C4; C-C8 cycloalkenyl or C7-C9 phenylalkyl. R4 represents a hydrogen atom or a residue a! ky! e in Ci-C, OH, -CHCN, alkoxy in C-Cig, cycloaicoxy in C-Ci, al! there! e, propargyl, acetety or phenylalkyl  <Desc / Clms Page number 41>    EMI41.1  enCy-C; R 1 A represents an oxygen atom, a residue-CR6 1 (6 0 0 0 0 Il h Il Il - CH2CH2-C-0-Y-0-C-CH, CH, - or- (CH-0- CZCO- (CH2) m-, \ X represents an oxygen atom or NR  EMI41.2  Y and Z independently of one another represent a C 1 -C alkylene radical, C 4 -C 12 alkylene interrupted by oxygen or N-R;  C-C8 alkenylene or phenylethylene, Rs and R independently of one another represent a hydrogen atom or a residue CF3, C1-C6 alkyl or phenyl, or else R and R form together with the carbon atom to which they are linked a nucleus C $ -Cg cycloalkylidene; R7 represents a hydrogen atom or a C1-C8 alkyl residue, Rg represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer from 2 to 6, and n represents a number from 2 to 15. 3. Compounds according to claim 1, in which R1 and R2 independently of one another represent a hydrogen atom or a C1-C8 alkyl, cyclohexyl or phenyl residue.  4. Compounds according to claim 1, in which R represents a hydrogen atom or a C1-C4 alkyl, C4-C16 alkoxy, C5-C8 cycloalkoxy, allyl, propargyl, acetyl or benzyl.  5. Compounds according to claim 1, in which RI and R2 independently of one another represent a hydrogen atom or a C1-C12 alkyl, C2-C12 alkenyl, C-C8 cycloalkyl, phenyl or benzyl, R4 represents a hydrogen atom or a C1-C4 alkyl, C-C1 alkoxy residue,  EMI41.3  Cs-C8 cycloalkoxy, allyl, propargyl, acetyl or benzyl;  EMI41.4  K.  UU '"" A represents a remainder "C -, - CHCH-COYOC-CHCH-ou 1 OO Il 0 K6 0 0 il il - (CH,), - 0-Z- (! -0- (CH,), -,  <Desc / Clms Page number 42>    EMI42.1  "X represents an oxygen atom or NR, Y and Z represent, independently of one another, a C-Cg alkylene, CC alkylene interrupted by oxygen; or C-Cg alkenylene, Rs and R6 independently of one another represent a hydrogen atom or a C1-C8 alkyl or phenyl residue, or else R5 and R6 form together with the carbon atom to which they are linked a C5-C8 cycloalkylidene ring ; R7 represents a hydrogen atom or a C1-C4 alkyl residue, m is an integer from 2 to 6, and n represents a number from 2 to 10.  6. Compounds according to claim 1, in which Ri and R2 independently of one another represent a hydrogen atom or a C1-C8 alkyl, cyclohexyl, phenyl or benzyl residue, R4 represents a hydrogen atom or a C1-C4 alkyl, C6-C12 alkoxy, acetyl or benzyl residue;  EMI42.2  U u 1 Il N A represents a residue-C-, or-CHCH-C-O-Y-O-C-CHCH-, R R6  EMI42.3  X represents an oxygen atom, Y represents a C2-C8 alkylene residue, C4-C12 alkylene interrupted by oxygen, Rs and R6 independently of one another represent a hydrogen atom or a residue C1-C8 alkyl, or else R5 and R6 form together with the carbon atom to which they are linked a C5-C8 cycloalkylidene ring; and n represents a number from 2 to 10.  7. Compounds according to claim 1, in which Ri represents a hydrogen atom,  EMI42.4  R2 represents a hydrogen atom or a C1-C4 alkyl or cyclohexyl residue, Rg is a hydrogen atom,  EMI42.5  Kt represents a hydrogen atom or a C1-C4 alkyl residue, 1 A represents a C-residue, 1 R6  EMI42.6  X represents an oxygen atom, R5 and R6 independently of one another represent a hydrogen atom or a C1-C4 alkyl residue, or else R5 and R <; together form with the carbon atom  <Desc / Clms Page number 43>  to which they are linked a cyclohexylidene ring; and n represents a number from 2 to 10.  8. Process for the preparation of 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 is reacted first  EMI43.1  wherein the generic symbols have the definition given in claim 1, with phosphorus trichloride to give a compound of formula VII  EMI43.2  wherein the generic symbols have the definition given in claim 1; and then reacting the compound of formula VII with a HALS type compound of formula V or a mixture of HALS type compounds of formula V  EMI43.3  wherein the generic symbols have the definition given in claim 1.  9. Oligomeric products obtainable by reaction of a bisphenol of formula VI or of a mixture of bisphenols of formula VI with phosphorus trichloride and a HALS type compound of formula V or a mixture of compounds of  <Desc / Clms Page number 44>  type HALS of formula V  EMI44.1  the generic symbols having the meaning given in claim 1.  10. Composition containing (a) an organic material exposed to degradation due to oxidation, heat or light and (b) at least one compound of formula 1 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 addition to constituents (a) and (b).  12. Composition according to claim 11, containing as other additives phenolic antioxidants, light stabilizers and / or shaping stabilizers.  13. Composition according to claim 11, containing as other additive at least one compound of the benzofuran-2-one type.  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 component (a) a polyolefin.  17. Composition according to claim 10, containing as constituent (a) polyethylene or polypropylene.  18. Use of the compounds having the formulas 1 and II defined in claim 1 and use of the oligomeric products defined in claim 9 as stabilizers of organic matter against degradation due to oxidation, heat or light.  19. Use according to claim 18 as shaping stabilizers (heat stabilizers) in thermoplastic polymers.  20. Method for stabilizing organic matter against degradation  <Desc / Clms Page number 45>  due to oxidation, heat or light, characterized in that at least one compound having the formula 1 or II defined in claim is incorporated into this material or in that it is applied to this material 1 or at least one oligomeric product according to claim 9.