DE3733423A1 - Heterocyclic compounds and their use as antioxidants - Google Patents

Abstract

Novel compounds of the formula I <IMAGE> are described. Y denotes -S- or -SO-, Z is -S-, -SO-, -SO2- or -CT1T2-, R1 stands for C1-C8-alkyl, C3-C4-alkenyl, unsubstituted or C1-C4-alkyl-substituted C5-C8-cycloalkyl, phenyl, tolyl or phenyl-C1-C3-alkyl, R2, R3 and R4 independently of one another denote hydrogen or a radical mentioned for R1, T1 is hydrogen, C1-C8-alkyl, C5-C8-cycloalkyl, phenyl or benzyl, and T2 denotes hydrogen or C1-C8-alkyl. The compounds of the formula I are suitable as antioxidants in organic polymers and in lubricants.

Description

The present invention relates to novel heterocyclic compounds, a process for their preparation and their Use as stabilizers for organic material.

S-containing heterocycles are described, for example, in D.C. DeJongh and R.Y. Van Fossen "Mass Spectra and Pyrolysis of o-phenylene sulfites and Related Compounds ", J. Org. Chem., Vol. 37, No. 8 (1972) Pp. 1129-1135, for example, biphenylylene-2,2'-sulfite and biphenylylene-2,2'-sulfate.

From F. R. Hewgill and J. M. Stewart: "On phenanthrene-4,5-quinones: a synthesis of morphenol ", Chem. Soc. Chem. Commun., 21 (1984), Pp. 1419-20 is alkyl-substituted dibenzo [d, f] [1,3,2] dioxathiepine oxide known.

Further, A. A. Gamble and J. G. Tillett: "Sulfur monoxide versus Sulfur dioxide elimination in cyclic aromatic sulfites ", Tetrahedron Letters, 42 (1970), pp. 3625-3628, a dichloro 12H-dibenzo [d, g] [1,3,2] dioxathiocin oxide.

Subject of the present invention are compounds of the formula I.

wherein
Y is -S- or -SO-,
Z is -S-, -SO-, -SO₂- or -CT₁T₂-,
R₁ is C₁-C₈alkyl, C₃-C₄alkanyl, unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl, phenyl, tolyl or phenyl-C₁-C₃alkyl,
R₂ R₃ and R₄ are independently hydrogen or have the meaning given for R₁,
T₁ is hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, phenyl or benzyl, and
T₂ is hydrogen or C₁-C₈-alkyl.

R₁, R₂, R₃, R₄, T₁ and T₂ as C₁-C₈ alkyl, for example Methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, 1,1-dimethylbutyl, n-heptyl, n-octyl or 2-ethylhexyl.

Preferably, R₁, R₂, R₃, R₄, T₁ and T₂ are C₁-C₄ alkyl, in particular Methyl, ethyl, isopropyl or t-butyl, and especially methyl or t-butyl (also called 1,1-dimethylethyl).

R₁, R₂, R₃ and R₄ as C₃-C₄-Akenyl mean z. Allyl, methallyl or propen-2-yl and especially allyl.

R₁, R₂, R₃, R₄, T₁ and T₂ as unsubstituted C₅-C₈-cycloalkyl For example, cyclopentyl, cyclohexyl or cycloheptyl or cyclooctyl. Preferred is cyclohexyl.  

R₁, R₂, R₃ and R₄ as C₁-C₄-alkyl-substituted C₅-C₈-cycloalkyl For example, methylcyclopentyl and especially Methylcyclohexyl.

R₁, R₂, R₃ and R₄ as phenyl-C₁-C₃-alkyl, for example, benzyl, α- methylbenzyl or α , α- dimethylbenzyl. Benzyl is preferred.

Preference is given to compounds of the formula I in which T₁ and T₂ are independent each other is hydrogen or C₁-C₄-alkyl.

Preference is furthermore given to compounds of the formula I in which Z is -CT₁T₂- or -S-, and especially those wherein T₁ and T₂ are independently each other is hydrogen or C₁-C₄-alkyl.

Of interest are compounds of formula I, wherein R₁ is C₁-C₄alkyl, C₃-C₄alkenyl, cyclohexyl, methylcyclohexyl, phenyl, α- methylbenzyl or α , α- dimethylbenzyl and R₂ is hydrogen.

Also of interest are compounds of formula I wherein R₂ and R₄ is hydrogen.

Particularly preferred compounds of the formula I, wherein R₁ and R₃ independently of one another C₁-C₄-alkyl, allyl, cyclohexyl, methylcyclohexyl or phenyl and R₃ additionally hydrogen and R₂ for Is hydrogen, in particular those in which Z is -S-, -CH₂-, -CH (C₁-C₄-alkyl) -, -C (C₁-C₄-alkyl) ₂-, R₁ C₁-C₄-alkyl or cycloalkyl, R₃ is hydrogen or C₁-C₄alkyl and R₄ is hydrogen or Methyl, and especially those in which Z is -CH₂-, -CH (CH₃) - or -C (CH₃) ₂-, R₁ and R₃ independently of one another C₁-C₄-alkyl or R₄ Mean hydrogen.

Also of particular interest are compounds of the formula I, wherein R₁ and R₃ allyl and R₂ and R₄ are hydrogen.  

Typical representatives of compounds of the formula I are the following:

4,8-bis (1 ', 1'-dimethylethyl) -dibenzo [d, g] [1,3,2] dioxathiocin 6-oxide, -
4,8-bis (1 ', 1'-dimethylethyl) -2,10-diethyl-dibenzo [d, g] [1,3,2] dioxath iocin-6-oxide;
4,8-bis (1 ', 1'-dimethylethyl) -1,11-dimethyl-dibenzo [d, g] [1,3,2] dioxat hiocin-6-oxide;
4,8-dicyclohexyl-2,10-dimethyl-dibenzo [d, g] [1,3,2] dioxathiocin 6-oxide;
2,4,8,10-tetrakis (1 ', 1'-dimethylethyl) -12-methyl-dibenzo [d, g] [1,3,2] -dioxathiocin-6-oxide;
2,4,8,10-tetramethyl-12-isopropyl-dibenzo [d, g] [1,3,2] dioxathiocin 6-oxide;
4,8-diallyl-dibenzo [d, g] [1,3,2] dioxathiocin-6-oxide;
2,4,8,10-Tetrallyl-dibenzo [d, g] [1,3,2] dioxathiocin-6-oxide;
4,8-bis (1 ', 1'-dimethylethyl) -2,10-dimethyl-dibenzo [d, g] [1,3,2] dioxat-hiocin;
4,8-bis (1 ', 1'-dimethylethyl) -2,10-diethyl-dibenzo [d, g] [1,3,2] dioxath-iocin;
4,8-dicyclohexyl-2,10-dimethyl-dibenzo [d, g] [1,3,2] dioxathiocin;
2,4,8,10-tetrakis (1 ', 1'-dimethylethyl) -12-methyl-dibenzo [d, g] [1,3,2] -dioxathiocin;
2,4,8,10-tetramethyl-12-isopropyl-dibenzo [d, g] [1,3,2] dioxathiocin;
2,4,8,10-Tetrallyl-dibenzo [d, g] [1,3,2] dioxathiocin;
4,8-diphenyl-dibenzo [d, g] [1,3,2] dioxathiocin;
4,8-bis (1 ', 1'-dimethylethyl) -2,10-dimethyl-dibenzo [d, g] [1,3,2] dioxad ithiocin-6-oxide;
2,4,8,10-tetrakis (1 ', 1'-dimethylethyl) -dibenzo [d, g] [1,3,2] dioxadithi OCIN-6-oxide;
4,8-di-tolyl-dibenzo [d, g] [1,3,2] dioxadithiocin-6-oxide;
4,8-diphenyl-dibenzo [d, g] [1,3,2] dioxadithiocin-6,6-dioxide;
4,8-dibenzyl-dibenzo [d, g] [1,3,2] dioxadithiocin 6-oxide.

In the known per se preparation of the invention Compounds of the formula I are, for example, so that one a compound of formula II  

wherein the symbols Z, R₁, R₂, R₃ and R₄ mentioned under formula I. Meaning, with a compound of formula III

Cl-Y-Cl (III)

in which Y has the meaning given in formula I, in the presence of a Base converts.

The phenols of formula II can also be used in the form of their alkali metal salts, such as B. Na⊕- and K⊕ salts present.

Suitable bases are organic and inorganic bases. suitable Organic bases are, for example, tertiary amines, such as Example triethylamine, pyridine or N, N-dimethylaniline. suitable inorganic bases, in solid or liquid form For example, sodium bicarbonate, potassium carbonate or alkali metal and alkaline earth hydroxides, such as sodium hydroxide or Potassium hydroxide.

The reaction may advantageously be below the boiling point of Thionyl chloride resp. Sulfur dichloride can be performed. Prefers is the temperature range from -20 ° to + 20 ° C, in particular 0 ° C-10 ° C.

The reaction can be carried out in the presence of a solvent. Suitable solvents are aliphatic, cycloaliphatic or aromatic hydrocarbons, such as hexane, cyclohexane or toluene, halogenated hydrocarbons, such as  Methylene chloride or chloroform, ethers, such as diethyl ether, Tetrahydrofuran or 1,2-dimethoxyethane, and polar aprotic Solvents, such as dimethylformamide.

The compounds of the formula I according to the invention are, for example from the organic phase, optionally by filtration and / or washing any accumulating hydrochlorides or separated from other solid residues, by evaporation of the Solvent (optionally at reduced pressure) isolated. you can by suitable cleaning methods, eg. B. recrystallization be further cleaned.

The starting materials of the formulas II and III are known compounds. They are commercially available or can be known Process are produced.

The compounds of the invention are effective stabilizers for organic materials which are resistant to thermal, oxidative or radiation-induced degradation are sensitive.

Another object of the invention is therefore the use of Compounds of the formula I according to the invention as stabilizers against thermal, oxidative or radiation-induced degradation in an organic material.

Preference is given to the use of the compounds of the invention Formula I as antioxidants in organic polymers, especially in Elastomers, or use in lubricants, eg. In Mineral oils or synthetic oils.

Examples of organic materials, which in the inventive Compounds of formula I are advantageously stabilized can, are:

• 1. Polymers of monoolefins and diolefins, for example polyethylene (which may optionally be crosslinked), polypropylene, polyisobutylene, Polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins, such as. B. of cyclopentene or norbornene.
• 2. mixtures of the polymers mentioned under 1), for. B. mixtures of Polypropylene with polyisobutylene.
• 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as B. ethylene-propylene copolymers, Propylene-butene-1 copolymers, propylene-isobutylene copolymers, Ethylene-butene-1 copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, Ethylene-alkyl acrylate copolymers, Ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers or ethylene-acrylic acid copolymers and their salts (ionomers), as well as Terpolymers of ethylene with propylene and a diene, such as hexadiene, Dicyclopentadiene or ethylidenenorbornene.
• 4. polystyrene, poly (p-methylstyrene).
• 5. Copolymers of styrene or α- methylstyrene with dienes or Acrylderivaen such. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength of styrene copolymers and another polymer such. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.
• 6. graft copolymers of styrene, such as. Styrene on polybutadiene, Styrene and acrylonitrile on polybutadiene, styrene and maleic anhydride on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene Propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates  or polyalkyl methacrylates, styrene and acrylonitrile Acrylate-butadiene copolymers, and their mixtures with the under 5) mentioned copolymers, as described for. B. as so-called ABS; MBS, ASA or AES polymers are known.
• 7. Halogen-containing polymers, such as. As polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, epichlorohydrin homo- and copolymers, in particular polymers containing halogens Vinyl compounds, such as. As polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, polyvinylidene fluoride; As well as their Copolymers such as vinyl chloride-vinylidene chloride, vinyl chloride Vinyl acetate or vinylidene chloride vinyl acetate.
• 8. Polymers derived from α , β- unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles.
• 9. Copolymers of the monomers mentioned under a) with each other or with other unsaturated monomers, such as. B. acrylonitrile-butadiene Copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile Alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
• 10. Polymers derived from unsaturated alcohols and amines or derive their acyl derivatives or acetals, such as polyvinyl alcohol, Polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, Polyallyl phthalate, polyallylmelamine.
• 11. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, Polyethylene oxide, polypropylene oxide or copolymers thereof with Bisglycidyl ethers.
• 12. polyacetals, such as polyoxymethylene, and also such polyoxymethylenes, the comonomers such. B. contain ethylene oxide.  
• 13. Polyphenyloxide and sulfides and their mixtures with styrene polymers.
• 14. Polyurethanes derived from polyethers, polyesters and polybutadienes with terminal hydroxyl groups on the one hand and aliphatic ones or aromatic polyisocyanates on the other hand derive and their Precursors.
• 15. polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding Derive lactams, such as polyamide 4, polyamide 6, polyamide 6/6, Polyamide 6/10, polyamide 11, polyamide 12, poly-2,4,4-trimethylhexamethylene terephthalamide, Poly-m-phenylene-isophthalamide, and their Block copolymers with polyethers such. With polyethylene glycol, Polypropylene glycol or polytetramethylene glycol.
• 16. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
• 17. Polyesters derived from dicarboxylic acids and dialcohols and / or derived from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, Polyhydroxybenzoates, as well as block Polyether esters derived from hydroxyl-terminated polyethers derived.
• 18. polycarbonates and polyestercarbonates.
• 19. Polysulfones, polyethersulfones and polyeterketones.
• 20. Crosslinked polymers derived from aldehydes on the one hand and Derive phenols, urea or melamine on the other hand, such as phenolic Formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
• 21. Drying and non-drying alkyd resins.  
• 22. Unsaturated polyester resins which are more saturated with copolyesters and unsaturated dicarboxylic acids with polyhydric alcohols, and derive vinyl compounds as crosslinking agents, as well their halogen-containing, flame-retardant modifications.
• 23. Crosslinkable acrylic resins derived from substituted acrylic acid esters derive such. As of epoxy acrylates, urethane acrylates or Polyester acrylates.
• 24. Alkyd resins, polyester resins and acrylate resins containing melamine resins, Urea resins, polyisocyanates, or epoxy resins crosslinked are.
• 25. Crosslinked epoxy resins derived from polyepoxides, e.g. B. of bis-glycidyl ethers or cycloaliphatic diepoxides.
• 26. Natural polymers, such as cellulose, natural rubber, gelatin, and their polymer homologue chemically modified derivatives, such as Cellulose acetates, propionates and butyrates, or the cellulose ethers, like methyl cellulose.
• 27. blends (polyblends) of the aforementioned polymers such as. B. PP / EPDM, polyamide 6 / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS.
• 28. Natural and synthetic organic matter, pure represent monomeric compounds or mixtures of such For example, mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic Esters (eg phthalates, adipates, phosphates or trimellitates), as well as Blends of synthetic esters with mineral oils in any Weight ratios, as z. B. as spin finishes application, as well as their aqueous emulsions.  
• 29. Aqueous emulsions of natural or synthetic rubbers, such as B. natural rubber latex or latices of carboxylated Styrene-butadiene copolymers.

The lubricants in question are familiar to the expert and z. B. in the "lubricant paperback" (Hüthig Verlag, Heidelberg, 1974).

The stabilizers according to the invention are the plastics or the lubricants useful in a concentration of 0.01-10% by weight, calculated on the material to be stabilized, added. Preferably, 0.05 to 5.0 wt .-%, especially preferably 0.1 to 2.0 wt .-% of the compounds of formula I, calculated on the material to be stabilized, incorporated into this.

The incorporation can be carried out, for example, by mixing in the process according to the invention Stabilizers and optionally further additives according to the methods customary in the art, before or during the Shaping, or by applying the dissolved or dispersed Compounds on the polymer, optionally with subsequent Evaporation of the solvent, take place. The invention Stabilizers can also be in the form of a masterbatch, the the stabilizer, for example in a concentration of 2.5 to Contains 25 wt .-% added to the plastics to be stabilized become.

The compounds of the formula I can also be used before or during the Polymerization or the crosslinking reaction are added. you thus receives directly stabilized polymers.

The materials stabilized in this way can be used in many different forms be applied, for. B. as films, fibers, tapes, molding compounds, Profiles or as a binder for paints, adhesives or putties.  

Another object of the present invention relates to compositions containing one against thermal, oxidative or radiation-induced degradation of sensitive organic material and as stabilizer at least one compound of formula I. Examples for such organic materials are enumerated above.

Preferred are compositions wherein the organic material a polymer, in particular an elastomer, is. As elastomers are particularly preferred:

Polydienes such as polybutadiene, polyisoprene or polychloroprene; Block polymers, such as styrene / butadiene / Styrene, styrene / isoprene / styrene or styrene / ethylene-propylene / styrene types; and acrylonitrile polymers.

These polymers can also be in the form of latices and can be stabilized as such.

Also preferred are compositions wherein the organic Material a lubricant, especially a synthetic lubricant or a mineral oil based lubricant.

In practice, the stabilizers according to the invention may be used together used with other stabilizers.

Lubricant formulations may additionally contain other additives included, which are added to certain performance characteristics to improve, such. Aminic antioxidants, metal passivators, Rust inhibitors, viscosity index improvers, pour point depressants, Dispersants / surfactants and anti-wear additives.

As further additives with which together the invention used stabilizers can be used are for example:

• 1. Antioxidants: 1.1. Alkylated monophenols:
  2,6-di-tert-butyl-4-methylphenol
  2-tert-butyl-4,6-dimethylphenol
  2,6-di-tert-butyl-4-ethylphenol
  2,6-di-tert-butyl-4-n-butylphenol
  2,6-di-tert-butyl-4-i-butylphenol
  2,6-di-cyclopentyl-4-methyl phenol
  2- ( α- methylcyclohexyl) -4,6-dimethylphenol
  2,6-di-octadecyl-4-methyl phenol
  2,4,6-tri-cyclohexylphenol
  2,6-di-tert-butyl-4-methoxymethylphenol1.2. Alkylated hydroquinones:
  2,6-di-tert-butyl-4-methoxyphenol
  2,5-di-tert-butyl-hydroquinone
  2,5-di-tert-amyl hyrochinon
  2,6-diphenyl-4-octadecyloxyphenol1.3. Hydroxylated thiodiphenyl ethers:
  2,2'-thio-bis- (6-tert-butyl-4-methylphenol)
  2,2'-thiobis (4-octylphenol)
  4,4'-thio-bis- (6-tert-butyl-3-methylphenol)
  4,4'-thio-bis- (6-tert-butyl-2-methylphenol) 1.4. Alkylidene bisphenols:
  2,2'-methylene-bis- (6-tert-butyl-4-methylphenol)
  2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol)
  2,2'-methylenebis [4-methyl-6- ( α- methylcyclohexyl) phenol]
  2,2'-methylenebis (4-methyl-6-cyclohexylphenol)
  2,2'-methylene-bis- (6-nonyl-4-methylphenol)
  2,2'-methylene-bis (4,6-di-tert-butylphenol)
  2,2'-ethylidene-bis (4,6-di-tert-butylphenol)
  2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol)
  2,2'-methylenebis [6- ( α- methylbenzyl) -4-nonylphenol]
  2,2'-Methylenebis [6- ( α , α -dimethylbenzyl) -4-nonylphenol]
  4,4'-methylene-bis (2,6-di-tert-butylphenol)
  4,4'-methylene-bis- (6-tert-butyl-2-methylphenol)
  1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane
  2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol
  1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane
  1,1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptob-utan
  Ethylene glycol-bis- [3,3-bis- (3'-tert-butyl-4'-hydroxyphenyl) butyrate] -
  Di- (3-tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadien
  Di- [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.1.5. benzyl:
  1,3,5-tri- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene
  Di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
  3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester
  Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate
  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
  3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid-dioctadecyl ester
  3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester,
  Calcium salz.1.6. Acylaminophenols:
  4-Hydroxy-lauric acid anilide
  4-hydroxy-stearic acid anilide
  2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine
  N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbaminsäureoctylester.1.7. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid
  with monohydric or polyhydric alcohols, such as. B. with methanol diethylene glycol octadecanol triethylene 1,6-hexanediol pentaerythritol neopentylglycol Tris-hydroxyethyl isocyanurate thiodiethylene Di-hydroxyethyl-oxamide 1.8. Esters of β - (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, such as. B. with methanol diethylene glycol octadecanol triethylene 1,6-hexanediol pentaerythritol neopentylglycol Tris-hydroxyethyl isocyanurate thiodiethylene Di-hydroxyethyl-oxamide 1.9. Amides of β - (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid such. B.
  N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylendia-min
  N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -trimethylendiam-in
  N, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazin1.10. Amine antioxidants:
  N, N'-di-isopropyl-p-phenylenediamine
  N, N'-di-sec-butyl-p-phenylenediamine
  N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine
  N, N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine
  N, N'-bis (1-methyl-heptyl) -p-phenylenediamine
  N, N'-diphenyl-p-phenylenediamine
  N, N'-di- (naphthyl-2) -p-phenylenediamine
  N-isopropyl-N'-phenyl-p-phenylenediamine
  N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine
  N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine
  N-cyclohexyl-N'-phenyl-p-phenylenediamine
  4- (p-toluene-sulfonamido) -diphenylamine
  N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine
  diphenylamine
  4-isopropoxy-diphenylamine
  N-phenyl-1-naphthylamine
  N-phenyl-2-naphthylamine
  octylated diphenylamine
  4-n-butylaminophenol
  4-butyrylamino-phenol
  4-Nonanoylamino-phenol
  4-Dodecanoylamino-phenol
  4-octadecanoylamino-phenol
  Di (4-methoxy-phenyl) -amine
  2,6-di-tert-butyl-4-dimethylamino-methyl-phenol
  2,4'-diaminodiphenylmethane
  4,4'-diamino-diphenylmethane
  N, N, N ', N'-tetramethyl-4,4'-diamino-diphenylmethane
  1,2-Di - [(2-methyl-phenyl) -amino] -ethane
  1,2-di- (phenylamino) -propane
  (O-tolyl) -biguanide
  Di- [4- (1 ', 3'-dimethyl-butyl) -phenyl] amine
• 2. UV absorber and light stabilizer: 2.1. 2- (2'-hydroxyphenyl) -benzotriazoles, such as. Example, the 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3-tetramethylbutyl) -, 5-chloro 3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy, 3 ', 5'-di-tert-amyl, 3', 5'-bis- ( α , α -dimethylbenzyl) derivative.2.2. 2-hydroxybenzophenones, such as. As the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4 , 4'-dimethoxy-Derivat.2.3. Esters of optionally substituted benzoic acids, such as. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di- tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.2.4. Acrylates, such as. B. α- cyano- β , β -diphenylacrylic acid ethyl ester or isooctyl ester, α- carbomethoxy-cinnamic acid methyl ester,
  α- cyano- β- methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,
  α- carbomethoxy-p-methoxy-cinnamic acid methyl ester,
  N- ( β- carbomethoxy- β- cyanovinyl) -2-methyl-indoline, 2.5. Nickel compounds, such as. B. nickel complexes of 2,2'-thio bis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands such n-butylamine, trietanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic monoalkyl esters such as methyl or ethyl esters, nickel complexes of ketoximes such as 2-hydroxy-4 -methylphenyl undecyl ketone oxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.2.6. Sterically hindered amines, such as. B. bis (2,2,6,6-tetramethylpiperidyl) sebacate,
  sebacate bis (1,2,2,6,6-pentamethylpiperidyl)
  N-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6 tetramethyl-4-hydroxypiperidine and succinic acid, condensation product of N, N '- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-t-octylamino-2,6-dichloro-1,3, 5-s-triazine,
  nitrilotriacetate tris (2,2,6,6-tetramethyl-4-piperidyl),
  Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetra carboxylic äure,
  1,1 '- (1,2-ethanediyl) -bis- (3,3,5,5-tetramethyl-piperazinone) .2.7. Oxidesäurediamide, such as. 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di tert -butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide, and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of ortho- and para-methoxy as well as of o- and p-ethoxy-di-substituted oxanilides.
• 3. Metal deactivators, such as. N, N'-diphenyloxalic diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis-salicyloylhydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-Salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic dihydrazide.
• 4. phosphites and phosphonites, such as. B. triphenyl phosphite, diphenylalkyl phosphites, Phenyldialkylposphite, tri (nonylphenyl) phosphite, Trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, Tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, -pentaerytritdiphosphit di- (2,4-di-tert-butylphenyl) Tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 3,9-bis (2,4-di-tert-butylphenoxy-2,4,8,10-tetraoxa-3,9-diphosphaspi-ro [5.5] undecane.
• 5. peroxide-destroying compounds, such as. B. esters of β- thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis- ( β- dodecylmercapto) - propionate.
• 6. polyamide stabilizers, such as. B. copper salts in combination with Iodides and / or phosphorus compounds and salts of divalent Manganese.
• 7. Basic co-stabilizers, such as. Melamine, polyvinylpyrrolidone, Dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine Derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts  higher fatty acids, for example, Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K-palmitate, antimony catechinate or tin catechinate.
• 8. nucleating agents, such as. B. 4-tert-butylbenzoic acid, adipic acid, Diphenyl.
• 9. Fillers and reinforcing agents, such as. Calcium carbonate, Silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulphate, Metal oxides and hydroxides, carbon black, graphite.
• 10. Other additives, such as. As plasticizers, lubricants, emulsifiers, Pigments, optical brighteners, flame retardants, antistatic agents, Propellant.
• 11. Metal passivators for copper, z. B .: Triazole, benzotriazole and their derivatives, 2-mercaptobenzothiazole, 2,5-dimercaptothiadiazole, salicylidene-propylenediamine, salts of Salicylaminoguanidine.
• 12. rust inhibitors:
  • a) Organic acids, their esters, metal salts and anhydrides, eg. For example: N-oleoyl sarcosine, sorbitan mono-oleate, lead naphthenate, dodecenyl succinic anhydride, alkenyl succinic acid half ester, 4-nonylphenoxyacetic acid.
  • b) nitrogen containing compounds, e.g. B .:
    • I. Primary, secondary or tertiary aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, eg. B. oil-soluble alkylammonium carboxylates.
    • II. Heterocyclic compounds, eg. B .:
      Substituted imidazolines and oxazolines.
  • c) Phosphorus-containing compounds, eg. B.: Amine salts of phosphoric acid partial esters.
  • d) Sulfur-containing compounds, for. B.: Barium dinonylnaphthalenesulfonates, calcium petroleum sulfonates.
• 13. Viscosity Index Improver:
  Polymethacrylates, vinylpyrrolidone / methacrylate copolymers, polybutenes, olefin copolymers, styrene / acrylate copolymers.
• 14. pour point depressants:
  Polymethacrylate, alkylated naphthalene derivatives.
• 15. Dispersants / surfactants:
  Polybutenylsuccinic imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenates.
• 16. Wear protection additives:
  Sulfur and / or phosphorus and / or halogen-containing compounds, such as sulfurized vegetable oils, zinc dialkyldithiophosphates, tritolyl phosphate, chlorinated paraffins, alkyl and aryl disulfides.

The following examples illustrate the invention.

Parts and percentages are given unless otherwise stated indicated on the weight.

Preparation Examples Example 1

8.7 g of thionyl chloride dissolved in toluene are dissolved within 25 minutes at 0 ° C-5 ° C to a solution of 17 g of 6,6'-bis (1,1-dimethylethyl) -4,4'-dimethyl-2,2'-methylene-bisphenol and 8.7 g of pyridine added dropwise in toluene. The solution is added after two hours of stirring Room temperature filtered and the filtrate was evaporated. After recrystallization the residue from 2-propanol gives 4,8-bis- (1 ', 1'-dimethylethyl) -2,10-dimethyl-dibenzo [d, g] [1,3,2] dioxathiocin - 6-oxide as a colorless powder; Mp 164 ° C; Yield: 12 g.

Calculated: S 8.29%
Found: S 8.10%
osmometric molecular weight determination (in CHCl₃): 380.

example 2

The procedure is as in Example 1, except that as bisphenol the corresponding amount (36.8 g) of 6,6'-bis (1 '', 1 '' - dimethylethyl) -4,4'- diethyl 2,2'-methylene-bisphenol and 4,8-bis (1 ', 1'-dimethylethyl) -2,10-diethyl-dibenzo [d, g] [1,3,2] dioxathiocin 6-oxide when receives colorless powder; Mp 141 ° -142 ° C; Yield: 21.6 g.

Calculated: S 7.73%
Found: S 7.58%.

example 3

The procedure is as in Example 1, except that as bisphenol the corresponding amount (34 g) of 6,6'-bis (1 '', 1 '' - dimethylethyl) -3,3'- dimethyl 2,2'-methylene-bisphenol and 4,8-bis (1 ', 1'-dimethylethyl) -1,11-dimethyl-dibenzo [d, g] [1,3,2] dioxate-hiocin 6-oxide as a colorless powder; Mp 157 ° -159 ° C; Yield: 24 g.

Calculated: S 8.29%
Found: S 8.22%.

example 4

The procedure is as in Example 1, except that as bisphenol the corresponding amount (35.9 g) of 6,6'-bis (1 '', 1 '' - dimethylethyl) -4,4'- dimethyl 2,2'-thiobisphenol and 4,8-bis (1 ', 1'-dimethylethyl) -2,10-dimethyl-dibenzo [d, g] [1,3,2] oxadio-xathiocin 6-oxide when receives colorless powder; Mp 187 ° C; Yield: 16.5 g.

Calculated: S 15.85%
Found: S 15.57%.

example 5

The procedure is as in Example 1, except that as bisphenol the corresponding amount (78.5 g) of 6,6'-dicyclohexyl-4,4'-dimethyl 2,2'-methylene-bisphenol and 4,8-dicyclohexyl-2,10-dimethyl dibenzo [d, g] [1,3,2] dioxathiocin 6-oxide as a colorless powder; Mp 188 ° C; Yield: 56 g.

Calculated: S 7.31%
Found: S 7.51%.

example 6

The procedure is as in Example 1, except that as bisphenol the corresponding amount (21.9 g) of 4,4 ', 6,6'-tetrakis (1' ', 1' '- dimethyl- ethyl) -2,2'-ethylidene bisphenol and 12-methyl-2,4,8,10-terakis (1 ', 1'-dimethyl) dibenzo [d, g] [1,3,2] dioxate -hiocin- 6-oxide as a colorless powder; Mp 187 ° C; Yield: 18.2 g.

Calculated: S 6.61%
Found: S 6.43%.

example 7

The procedure is as in Example 1, except that as bisphenol the corresponding amount (29.8 g) of 4,4 ', 6,6'-tetramethyl-2,2' - (2 '' - propylidene) bisphenol and 12- (1'-methylethyl) -2,4,8,10- tetramethyldibenzo [d, g] [1,3,2] dioxathiocin 6-oxide as colorless Receives powder; Mp 205 ° -207 ° C; Yield: 10.6 g.

Calculated: S 9.31%
Found: S 9.35%.

example 8

The procedure is as in Example 1, except that as bisphenol the corresponding amount (31.25 g) of 6,6'-bis (1 '', 1 '' - dimethylethyl) -2,2'-methylenebisphenol and 4,8-bis (1 ', 1'-dimethylethyl ) dibenzo [d, g] [1,3,2] dioxathiocin 6-oxide as a colorless powder obtained; Mp 109 ° -111 ° C; Yield: 24.2 g.

Calculated: S 8.94%
Found: S 8.88%.

example 9

10.5 g sulfur dichloride, dissolved in toluene, within 60 minutes at 0 ° -5 ° C to a solution of 34.0 g of 6,6'-bis (1 '', 1 '' - dimethylethyl) 4,4'-dimethyl-2,2'-methylene-bisphenol-1 and 17 g of pyridine in Toluene added dropwise. The solution is added after two hours of stirring Room temperature filtered and the filtrate was evaporated. After recrystallization the residue from 2-propanol gives 4,8-bis- (1 ', 1'-dimethylethyl) 2,10-dimethyl-dibenzo [d, g] [1,3,2] dioxathiocin as a colorless powder; Mp 180 ° -182 ° C; Yield: 11.9 g.

Calculated: S 8.65%
Found: S 8.68%.
osmometric molecular weight determination (in CHCl₃): 367.

example 10

The procedure is as in Example 9, except that as bisphenol the corresponding amount (36.8 g) of 6,6'-bis (1 '', 1 '' - dimethylethyl) -4,4'- diethyl 2,2'-methylene-bisphenol and 4,8-bis (1 ', 1'-dimethylethyl-2,10-diethyl-dibenzo [d, g] [1,3,2] dioxathoicin as colorless Receives powder; Mp 134 ° -135 ° C; Yield: 11.2 g.

Calculated: S 8.04%
Found: S 8.35%.

example 11

The procedure is as in Example 9, except that as bisphenol the corresponding amount (27.5 g) of 6,6'-dicyclohexyl-4,4'-dimethyl 2,2'-methylene-bisphenol and 4,8-dicyclohexyl-2,10-dimethyl dibenzo [d, g] [1,3,2] dioxathiocin as a colorless powder; Mp 181 ° C; Yield: 14.5 g.

Calculated: S 7.59%
Found: S 7.41%.

example 12

The procedure is as in Example 9, except that as bisphenol the corresponding amount (35.1 g) of 4,4 ', 6,6'-tetrakis (1' ', 1' '- dimethyl- ethyl) -2,2'-ethylidene bisphenol and 12-methyl-2,4,8,10- tetrakis (1 ', 1'-dimethylethyl) dibenzo [d, g] [1,3,2] dioxathiocin receives colorless powder; Mp 237 ° C (after column chromatography); Yield: 12.45 g.

Calculated: S 6.84%
Found: S 7.07%.

example 13

The procedure is as in Example 9, except that as bisphenol the corresponding amount (29.8 g) of 4,4 ', 6,6'-tetramethyl-2,2' - (2 '' - propylidene) bisphenol and 12- (1'-methylethyl) -2,4,8,10-teramethyl-dibenzo [d, g] [1,3,2] dioxathi-ocine as a colorless powder obtained; Mp 184 ° -186 ° C; Yield: 16.6 g.

Calculated: S 9.76%
Found: S 9,89%.

Claims (17)

1. Compounds of the formula I wherein
Y is -S- or -SO-,
Z is -S-, -SO-, -SO₂- or -CT₁T₂-,
R₁ is C₁-C₈alkyl, C₃-C₄alkanyl, unsubstituted or C₁-C₄alkyl-substituted C₅-C₈cycloalkyl, phenyl, tolyl or phenyl-C₁-C₃alkyl,
R₂ R₃ and R₄ are independently hydrogen or have the meaning given for R₁,
T₁ is hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, phenyl or benzyl, and
T₂ is hydrogen or C₁-C₈-alkyl. 2. Compounds of the formula I according to claim 1, characterized gekennzeicnet, that T₁ and T₂ are independently hydrogen or C₁-C₄alkyl. 3. Compounds of the formula I according to claim 1, characterized in that that Z is -CT₁T₂- or -S-. 4. Compounds of the formula I according to claim 3, characterized in that that T₁ and T₂ are independently hydrogen or C₁-C₄alkyl.   5. Compounds of formula I according to claim 3, characterized in that R₁ is C₁-C₄-alkyl, C₃-C₄-alkenyl, cyclohexyl, methylcyclohexyl, phenyl, α- methylbenzyl or α , α- dimethylbenzyl and R₂ is hydrogen. 6. Compounds of the formula I according to claim 5, characterized in that that R₂ and R₄ are hydrogen. 7. Compounds of the formula I according to claim 1, characterized in that R₁ and R₃ independently of one another are C₁-C₄-alkyl, allyl, Cyclohexyl, methylcyclohexyl or phenyl and R₃ additionally hydrogen mean and R₂ is hydrogen. 8. Compounds of the formula I according to claim 7, characterized in that Z is -S-, -CH₂-, -CH (C₁-C₄-alkyl) -, -C (C₁-C₄-alkyl) ₂-, R₁ is C₁-C₄ alkyl or cyclohexyl, R₃ is hydrogen or C₁-C₄ alkyl and R₄ is hydrogen or methyl. 9. Compounds of the formula I according to claim 8, characterized in that in that Z is -CH₂-, -CH (CH₃) - or -C (CH₃) ₂, R₁ and R₃ independently of one another are C₁-C₄-alkyl and R₄ is hydrogen. 10. Compounds of the formula I according to claim 1, characterized in that R₁ and R₃ are allyl and R₂ and R₄ are hydrogen. 11. A process for the preparation of compounds of the formula I according to claim 1, characterized in that a compound of the formula II wherein the symbols, Z, R₁, R₂, R₃ and R₄ have the meaning given in claim 1, with a compound of formula III Cl-Y-Cl (III) wherein Y has the meaning given in claim 1, in the presence of a base , 12. Use of the compounds of the formula I according to claim 1 as Stabilizers against thermal, oxidative or radiation-induced Removal in an organic material. 13. Use of the compounds of the formula I according to claim 12, characterized in that the organic material is an organic Polymer is. 14. Use of the compounds of the formula I according to claim 13, characterized in that the organic material is a Lubricant is. 15. Compositions containing an anti-thermal, oxidative or radiation-induced degradation of sensitive organic matrial and at least one compound of the formula I according to claim 1. 16. Compositions according to claim 15, characterized the organic material is an organic polymer. 17. Compositions according to claim 15, characterized that the organic material is a lubricant.