EFFICIENT PHOSPHORUS-CONTAINING STABILIZERS BASED ON DIPHENYLAMINE AND HETEROCYCLICAL DIPHENYLAMINE DERIVATIVES

Abstract

The present invention relates to the use of efficient phosphorous substances, in particular based on diphenylamine and heterocyclic diphenylamine derivatives as stabilisers for organic materials, in particular for plastic materials, against oxidative, thermal and / or actinic degradation. The present invention also relates to an organic material which is correspondingly stabilised as described above. The invention also relates to a method for stabilising organic materials, and specific stabilisers.

Description

[0001] Efficient phosphorus-containing stabilizers based on diphenylamine and heterocyclic diphenylamine derivatives

[0002] The present invention relates to the use of efficient phosphorus-containing substances, particularly those based on diphenylamine and heterocyclic diphenylamine derivatives, as stabilizers for organic materials, especially plastic materials, against oxidative, thermal, and / or actinic degradation. The present invention also relates to an organic material stabilized as described above. Furthermore, the invention relates to a method for stabilizing organic materials and to specific stabilizers.

[0003] Plastics and plastic-based compositions, such as coatings, are subject to autoxidation during processing and use. This leads to changes in the polymer chain, such as in molecular weight or the formation of new chemical groups, starting from radical chain scission through mechanochemical processes or through UV radiation in the presence of oxygen.

[0004] The breakdown or chemical alteration of polymer molecules impairs the mechanical properties of plastics and leads to color changes (yellowing) or other undesirable effects. Thermal degradation limits the maximum operating temperature of plastics, and aging processes restrict the possible service life of plastic objects, which is shortened with increasing temperature.

[0005] Therefore, the addition of special stabilizers such as antioxidants and

[0006] Light stabilizers are required, which delay degradation processes and thus have a significant impact on the processability and range of applications of plastics. Currently, there is great interest in more effective stabilizers or...

[0007] Stabilizer systems are needed, among other reasons, because plastics are increasingly used in applications where they are exposed to increased thermal or mechanical stresses (electromobility, lightweight construction, high-performance batteries, etc.). Another reason to search for new stabilizers is that many currently used substances do not meet all requirements, for example, regarding their compatibility with the polymers to be protected, low migration, or the formation of undesirable degradation products. There are various types of stabilizers, of which the following are particularly important:

[0008] Processing stabilizers slow down the degradation processes that occur at high processing temperatures.

[0009] Long-term thermal stabilizers are used to delay aging, especially at elevated temperatures.

[0010] High-temperature stabilizers counteract degradation when plastics are exposed to high temperatures (180°C and above).

[0011] UV stabilizers delay or prevent degradation processes initiated by UV light. In many cases, the various stabilizers are used in (synergistic) combinations. The function of stabilizers includes, among other things, neutralizing free radicals and deactivating peroxides and hydroperoxides formed upon exposure to oxygen, as these damage the polymer chain. The effectiveness of stabilizers and antioxidants is crucial for both the processability of the plastics and the lifespan of the objects manufactured from them. They also influence the maximum operating temperature of the plastics and their potential service life at elevated temperatures.

[0012] Numerous chemical compounds are available on the market as stabilizers / antioxidants. The most important classes of antioxidants are sterically hindered phenols, phosphites or phosphonites, amines, thio compounds, hydroxylamines, and lactones. Sterically hindered amines, so-called HALS compounds, are particularly noteworthy as light stabilizers that also function as long-term heat stabilizers. Benzotriazoles, benzophenones, hydroxyphenyltriazines, and others are also frequently used as UV absorbers.

[0013] The particular importance of phosphite stabilizers stems from their ability to deactivate peroxides and hydroperoxides. However, the substances used so far have disadvantages, including limitations in thermostability, long-term effectiveness, hydrolysis resistance, and compatibility. Therefore, intensive research is underway to find new, improved stabilizers that offer advantages such as:

[0014] Increased hydrolysis resistance and improved thermal properties

[0015] Suitable for use at particularly high temperatures;

[0016] exceptionally high and long-lasting efficiency;

[0017] no unwanted side effects (discoloration, etc.).

[0018] For elastomers, diphenylamine derivatives are used as environmentally friendly, low-toxicity stabilizers. The structurally similar, heterocyclic compound phenothiazine also possesses a high capacity to deactivate radicals and is only slightly toxic. It is used for the storage stabilization of acrylates, methacrylates, and other monomers, where it prevents the spontaneous polymerization of radicals by scavenging them, thus acting similarly to plastic stabilizers. Furthermore, phenothiazine is an effective antioxidant for lubricants. A patent from 1961 (GB 4331, "Phenothiazine stabilizers for Polyethylene") describes the use of phenothiazine as a stabilizer for polyethylene.Despite its proven stabilizing effect on thermoplastic polymers and elastomers, phenothiazine has the disadvantage of high volatility under normal processing conditions and therefore has no commercial significance as a plastic stabilizer.

[0019] To date, very few phosphorus-containing phenothiazine derivatives have been described or listed in patents. Phenothiazine derivatives bearing phosphorus substituents on the nitrogen atom are mentioned in the following patents: WO2015158692A1 (2016), WO2015158689A1 (2016), CN 101531578A (2009).

[0020] The patent JP2006328100A (Songwon Industrial Co. LTD, 2006) mentions the following compound as a flame retardant for plastics:

[0021]

[0022] However, until now nothing was known regarding the antioxidant stabilization effect of this compound and other phosphorus-containing derivatives of phenothiazine.

[0023] Numerous phosphorus-containing derivatives of the structurally related carbazole have been described, and various applications of such substances are listed in patent literature, but not as a stabilizer for plastics.

[0024] There is no information available regarding the use or testing of phosphorus-containing diphenylamine derivatives, which have at least one carbon atom attached to the phosphorus atom, as stabilizers for plastics.

[0025] The object of the present invention was to develop new effective stabilizers for plastics and plastic-based applications.

[0026] This problem is solved with regard to the use of specific materials as stabilizers with the features of claim 1, with regard to a specifically stabilized organic material with the features of claim 13, with regard to a method for stabilizing organic materials with the features of claim 14, and with regard to specific stabilizers with the features of claim 15. The respective dependent claims represent advantageous further developments.

[0027] The present invention thus relates to the use of a compound or mixtures of several compounds according to general formula I

[0028] A-By

[0029] Formula 1

[0030] where

[0031] Fragment A has the following meaning

[0032]

[0033] each independently of each other

[0034] X is a sulfur atom

[0035] n is 0 or 1,

[0036] x 0 or 1, Z 1 and Z 2 are selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, heterocyclic groups, wherein one or more further fragments A and / or B may be bonded to the aforementioned groups,

[0037] as well as a group -OZ 3 , where Z 3 selected from alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, as well as heterocyclic groups, and a grouping -SZ 4 , where Z 4 is selected from alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, and heterocyclic groups, where in the case x = 1 the groups are Z 1 and Z 2 together with the phosphorus atom they can form a ring system to which one or more further fragments A and / or B may be bonded,

[0038] fragment B has the following meaning

[0039] each independently of each other

[0040] R 1 to R 10 are selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and heterocyclic groups, wherein (in the case y = 1 or 2), preferably in the case y = 1, the groups R 1 and R 6 can also be connected via a grouping -Y- linking the phenyl groups, where Y is selected from the group consisting of S, O, NH, PH and a covalent bond,

[0041] where fragments A and B are connected to each other by covalent bonding of the phosphorus and nitrogen atoms,

[0042] and where y is 1 or 2,

[0043] where x + y = 2,

[0044] For the stabilization of organic materials, especially against oxidative, thermal, and / or actinic degradation. The compound according to general formula I can exist as a separate molecule, but also bound to a polymeric framework, either within the main chain or in a side chain.

[0045] Preferably Z 1 and Z 2 selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, heterocyclic groups, wherein one or more further fragments A and / or B may be bonded to the aforementioned groups,

[0046] as well as a group -OZ 3 , where Z 3 is selected from alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, and heterocyclic groups, where in the case x = 1 the groups are Z 1 and Z 2together with the phosphorus atom they can form a ring system to which one or more further fragments A and / or B may be bound.

[0047] Surprisingly, it was found that the compounds, as defined above according to the general formula I, exhibit particularly good efficiency as stabilizers of organic materials, so that their use leads to high stabilization rates even at relatively low concentrations.

[0048] In particular, the compounds described above are suitable for stabilizing plastics, coatings, lubricants, hydraulic oils, chemicals, and monomers.

[0049] In the compounds described above according to formula I, it is particularly preferred if fragment A is selected from the following residues.

[0050] each independently of each other

[0051] R 11selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and heterocyclic groups,

[0052] R 12 selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, heterocyclic groups, wherein the aforementioned groups may also have heteroatoms and / or one or more further fragments A and / or B may be bonded to the aforementioned groups, and

[0053] X and n are as defined in claim 1. Fragment A is particularly preferably selected from the following residues.

[0054]

[0055] where x = y = 1 in each case,

[0056]

[0057] where x = 0 and y = 2 in each case, and

[0058]

[0059] where x = y = 1 in each case.

[0060] With regard to fragment B, it is advantageous if it is selected from the group consisting of the following residues.

[0061] where y = 1 or 2,

[0062] where y = 1 or 2, as well as where y = 1 or 2 where each is independent of each other R 2 to R 5 and R 7 to R 10 and Y as defined in claim 1.

[0063] It is particularly advantageous if fragment B is selected from the group consisting of the following residues.

[0064] Particularly preferred compounds that can be used as stabilizers for the purposes of the present invention are listed below:

[0065] 12

[0066] 13

[0067] each independently of each other

[0068] R 11selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and heterocyclic groups.

[0069] Due to insufficient efficiency, a compound according to the following formula is particularly problematic.

[0070] Ph2N-P(OPh)2 is preferably excluded from use according to the present invention.

[0071] The compound according to general formula I, or in the case of a mixture of several compounds according to general formula I, the entirety of all compounds according to general formula I, are preferably added (incorporated) and / or incorporated by mixing into the organic material, i.e., the material that is subject to oxidative, thermal, and / or actinic degradation, at a weight fraction of 0.01 to 10 wt.%, more preferably 0.05 to 5 wt.%, and particularly preferably 0.1 to 1.5 wt.%. Particularly in the case of plastic compositions, this can be achieved, for example, during thermal processing by melting, such as by kneading or extrusion of these materials. In the case of liquid materials, such as oils, the compounds according to general formula I are incorporated by dissolving or dispersing the materials in the liquids.

[0072] In the event that the compound according to general formula I is used for stabilizing plastic materials, it is preferred that the plastic be selected from the group consisting of polymers of olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with, for example, 5-ethylidene-2-norbornene as a comonomer, ethylene-vinyl acetate (EVA), ethylene acrylates, such as ethylene butyl acrylate, ethylene acrylic acid and their salts (ionomers), as well as terpolymers such as... Ethylene acrylic acid glycidyl (meth)acrylate, graft polymers such as e.g.Polypropylene graft maleic anhydride, polypropylene graft acrylic acid, polyethylene graft acrylic acid, polyethylene polybutyl acrylate graft maleic anhydride, and blends such as LDPE / LLDPE or long-chain branched polypropylene copolymers produced with alpha olefins as comonomers, such as 1-butene, 1-hexene, 1-octene or 1-octadecene.

[0073] polystyrene, polymethylstyrene, poly-alpha-methylstyrene,

[0074] Polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile (SAN), styrene-acrylonitrile acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives such as polyvinylcyclohexane

[0075] halogen-containing polymers such as polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo and copolymers especially with ethylene oxide (ECO)

[0076] Polymers of unsaturated esters such as polyacrylates and polymethacrylates like polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, copolymers such as polyacrylonitrile-polyalkyl acrylate,

[0077] Polymers made from unsaturated alcohols and derivatives, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine

[0078] Polyacetals, such as polyoxymethylene (POM) or copolymers with, for example, butanal,

[0079] Polyphenylene oxides and blends with polystyrene or polyamides,

[0080] Polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,

[0081] Polytetrahydrofuran

[0082] Polyurethanes, made from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6-toluene diisocyanate or methylene diphenyl diisocyanate, in particular also linear polyurethanes (TPU), polyureas,

[0083] Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12, as well as (partially) aromatic polyamides such as polyphthalamides, e.g., produced from terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylenediamine or m-xylylenediamine, or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6, or blends of polyamides and polyolefins such as PA / PP.

[0084] Polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether) ketones, polysulfones, polyethersulfones, polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins,

[0085] Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthylate (PEN), poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetramethylene succinate, polycaprolactone; polycarbonates, polyester carbonates, and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA

[0086] n) Cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate,

[0087] o) Epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with, for example, hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically acting hardeners,

[0088] p) Phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins,

[0089] q) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds, e.g., styrene, alkyd resins,

[0090] r) Silicones, e.g. based on dimethylsiloxanes, methylphenylsiloxanes or diphenylsiloxanes, e.g. vinyl groups terminated s) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

[0091] If the polymers listed under a) to r) are copolymers, they can exist in the form of random, block, or tapered structures. Furthermore, the polymers mentioned can exist in the form of linear, branched, star-shaped, or hyperbranched structures.

[0092] If the polymers listed under a) to r) are stereoregular polymers, they can be in the form of isotactic, stereotactic, but also atactic forms or as stereoblock copolymers.

[0093] Furthermore, the polymers listed under a) to r) can exhibit both amorphous and (partially) crystalline morphologies.

[0094] The polyolefins mentioned under a) may also be cross-linked, e.g. cross-linked polyethylene, which is then referred to as X-PE.

[0095] The polymers mentioned a) to r) can be present not only as new products but also in the form of recyclates, e.g. as production waste or from recycling collections (“post-consumer” recyclates).

[0096] For the conceptual definition of recycled plastics, in a further preferred embodiment, the terms recycled plastics or recycled plastics are used. For this conceptual definition, reference is made to the standard DIN EN 15347:2007, which defines the term recycled plastic. This definition is also used as the basis for the present invention.

[0097] Particularly preferred is the recycled plastic selected from the group consisting of recycled polyesters, in particular recycled polyethylene terephthalate (rPET), recycled polybutylene terephthalate (rPBT), recycled polylactic acid (rPLA), recycled polyglycolide and / or recycled polycaprolactone; recycled polyolefins, in particular recycled polypropylene (rPP), recycled polyethylene and / or recycled polystyrene (rPS); recycled polyvinyl chloride (rPVC), recycled polyamides and mixtures and combinations thereof.

[0098] Many recycled plastics are subject to relevant international standards. For example, DIN EN 15353:2007 applies to recycled PET plastics. Recycled PS is described in more detail in DIN EN 15342:2008. Recycled PE is covered in DIN EN 15344:2008. Recycled PP is covered in

[0099] DIN EN 15345:2008 characterizes PVC recyclates. PVC recyclates are further specified in DIN EN 15346:2015. For the purpose of defining the corresponding specific plastic recyclates, this patent application adopts the definitions of these international standards.

[0100] Furthermore, the compounds present can be used to stabilize rubbers and elastomers. These can be natural rubber (NR) or synthetic rubber materials. If the organic materials are oils and fats, they can be based on mineral oils, vegetable fats, or animal fats, or they can be oils, fats, or waxes based on, for example, synthetic esters. Examples of vegetable oils and fats are palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower oil, and castor oil. Animal fats include, for example, fish oils or beef tallow.

[0101] Furthermore, the compounds according to the invention can be used to stabilize low-molecular-weight or oligomeric polyols, such as those used in polyurethane production. Suitable hydroxy compounds include, for example, butane-1,4-diol, oligomeric ethylene glycols, or tetrahydrofuran oligomers.

[0102] The compounds according to the invention can also be used as stabilizers for lubricants, hydraulic oils, engine oils, turbine oils, gear oils, metalworking fluids, or as lubricating greases. These mineral or synthetic lubricants are predominantly based on hydrocarbons.

[0103] It is possible and advantageous for the plastic, for example the plastic molding compound, to contain at least one further additive selected from the group consisting of UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact improvers, plasticizers, lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, marking agents and antifogging agents.

[0104] Possible further additives are selected from the groups of UV absorbers, light stabilizers, stabilizers, hydroxylamines, benzofurans, nucleating agents, impact enhancers, plasticizers, lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, marking agents, or antifogging agents. In a preferred embodiment, the compositions contain, in particular, acid scavengers, e.g., based on salts of long-chain acids such as calcium stearate, magnesium stearate, zinc stearate, calcium lactate, or hydrotalcites.In a further preferred embodiment, the compositions contain stabilizers from the group of phenolic antioxidants and phosphites / phosphonites, hydroxylamines, amines, lactones, thio compounds and / or.

[0105] Light stabilizers from the group of hindered amines (HALS) and / or UV absorbers.

[0106] Suitable light stabilizers include, for example, compounds based on 2-(2 ' -Hydroxyphenyl)-benzotriazoles, 2-Hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-Hydroxyphenyl)-1,3,5-triazines.

[0107] Suitable 2-(2 '-Hydroxyphenyl)benzotriazole sind beispielsweise 2-(2'- Hydroxy-5'methylphenyl)benzotriazol, 2-(3',5'-Di-tert-butyl-2'-hydroxy- phenyl)benzotriazol, 2-(5'-tert-Butyl-2'-hydroxy-phenyl)benzotriazol, 2-(2'- Hydroxy-5'-(l,l,3,3-tetramethylbutyl)phenyl)benzotriazol, 2-(3',5'-Di-tert- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'- methylphenyl-5-chlorobenzotriazol, 2-(3'-sec-Butyl-5'-tert-butyl-2'-hydroxy- phenyl)benzotriazol, 2-(2'-Hydroxy-4'-octyloxyphenyl)benzotriazol, 2-(3',5'-Di- tert-amyl-2'-hydroxyphenyl)benzotriazol, 2-(3',5'-Bis(a,a-dimethylbenzyl)-2'- hydroxyphenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxy- carbonylethyl)phenyl)-5-chlorobenzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethyl- hexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazol, 2-(3'-tert- Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl) phenyl)-5-chlorobenzotriazol,

[0108] 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazol, 2-(3'-tert-Butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl)benzotriazol, 2-(3'-tert-Butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)- benzotriazol, 2-(3'-Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazol, 2-(3'- tert-Butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazol, 2,2'-

[0109] Methylenbis [4-(l,l,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; das Produkt der Umesterung von 2-[3'-tert-Butyl-5'-(2-methoxycarbonylethyl)-2'- hydroxyphenyl]-2H-benzotriazol mit Polyethylenglycol 300; [R— CH2CH2— COO— CH2CH2-]-2, wobei R = 3'-tert-Butyl-4'-hydroxy-5'-2H-benzotriazol-2- ylphenyl, 2-[2'-Hydroxy-3'-(a,a-dimethylbenzyl)-5'-(l,l,3,3-tetramethylbutyl)- phenyl] benzotriazol, 2-[2'-hydroxy-3'-(l,l,3,3-tetramethylbutyl)-5'-(a,a- dimethylbenzyl)phenyl]benzotriazol.

[0110] Geeignete 2-Hydroxybenzophenone sind beispielsweise 4-Hydroxy-, 4- Methoxy-, 4-Octyloxy-, 4-Decyloxy- 4-Dodecyloxy, 4-Benzyloxy, 4,2',4'- Trihydroxy- und 2'-Hydroxy-4,4'-dimethyoxy-Derivate der 2-Hydroxybenzophenone.

[0111] Geeignete Acrylate sind beispielsweise Ethyl-a-cyano-ß,ß-diphenylacrylat, lsooctyl-a-cyano-ß,ß-diphenylacrylat, Methyl-a-carbomethoxycinnamat, Me- thyl-a-cyano-ß-methyl-p-methoxycinnamat, Butyl-a-cyano-ß-methyl-p- methoxycinnamat, Methyl-a-carbomethoxy-p-methoxycinnamat und N-(ß- carbomethoxy-ß-cyanovinyl)-2-methylindolin.

[0112] Suitable esters of benzoic acids include, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octa-decyl-3,5-di-tert-butyl-4-hydroxybenzoate, and 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

[0113] Suitable oxamides include, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxy-oxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)-oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0114] Geeignete 2-(2-Hydroxyphenyl)-l,3,5-Triazine sind beispielsweise 2,4,6-Tris(2- hydroxy-4-octyloxyphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6- bis(2,4-dimethylphenyl)-l,3,5-triazin, 2-(2,4-Dihydroxyphenyl)-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazin, 2,4-Bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4- dimethylphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl-l,3,5-triazin, 2-(2-Hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazin, 2-(2-Hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-butyloxypropoxy)- phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3- octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-l,3,5-triazin, 2-[4-(Dodecyl- oxy / Tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethyl- phenyl)-l,3,5-triazin, 2-[2-Hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)- phenyl]-4,6-bis(2,4-dimethylphenyl-l,3,5-triazin, 2-(2-Hydroxy-4-hexyloxy)- phenyl-4,6-diphenyl-l,3,5-triazin, 2-(2-Hydroxy-4-methoxyphenyl)-4,6- diphenyl-l,3,5-triazin, 2,4,6-Tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)- phenyl]-l,3,5-triazin, 2-(2-Hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1,3,5-triazin, 2-{2-Hydroxy-4-[3-(2-ethylhexyl-l-oxy)-2-hydroxypropyloxy]- phenyl}-4,6-bis(2,4-dimethylphenyl-l,3,5-triazin.,

[0115] Geeignete phenolische Antioxidantien sind beispielsweise:

[0116] Alkylierte Monophenole, wie z.B. 2,6-Di-tert-butyl-4-methylphenol, 2-tert- Butyl-4,6-dimethylphenol, 2,6-Di-tert-butyl-4-ethylphenol, 2,6-Di-tert-butyl-4- n-butylphenol, 2,6-Di-tert-butyl-4-isobutylphenol, 2,6-Dicyclopentyl-4-methyl- phenol, 2-(a-Methylcyclohexyl)-4,6-dimethylphenol, 2,6-Dioctadecyl-4- methylphenol, 2,4,6-Tricyclohexylphenol, 2,6-Di-tert-butyl-4-methoxymethyl- phenol, lineare oder verzweigte Nonylphenole, wie z.B. 2,6-Dinonyl-4-methyl- phenol, 2,4-Dimethyl-6-(l'-methylundec-l'-yl)phenol, 2,4-Dimethyl-6-(l'- methylheptadec-l'-yl)phenol, 2,4-Dimethyl-6-(l'-methyltridec-l'-yl)phenol und Mischungen hiervon;

[0117] Alkylthiomethylphenole, wie z.B. 2,4-Dioctylthiomethyl-6-tert-butylphenol, 2,4-Dioctylthiomethyl-6-methylphenol, 2,4-Dioctylthiomethyl-6-ethylphenol, 2,6-Didodecylthiomethyl-4-nonylphenol;

[0118] Hydroquinones and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methyloxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipate; tocopherols, such as α-, β-, γ-, δ-tocopherol and mixtures thereof (vitamin E); hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-secamylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; Alkylidenebisphenols, such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclhexylphenol), 2,2'-Methylenbis(6-nonyl-4-methylphenol), 2,2'-Methylenbis(4,6-di-tert- butylphenol), 2,2'-Ethylidenbis(4,6-di-tert-butylphenol), 2,2'-Ethylidenbis(6- tert-butyl-4-isobutylphenol), 2,2'-Methylenbis[6-(a-methylbenzyl)-4-nonyl- phenol], 2,2'-Methylenbis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'- Methylenbis(2,6-di-tert-butylphenol, 4,4'-Methylenbis(6-tert-butyl-2- methylphenol), l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan, 2,6- Bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, l,l,3-Tris(5-tert- butyl-4-hydroxy-2-methylphenyl)butan, l,l-bis(5-tert-butyl-4-hydroxy-2- methylphenyl)-3-n-dodecylmercaptobutan, Ethylenglycol-bis[3,3-bis(3'-tert- butyl-4'-hydroxyphenyl)butyrat], Bis(3-tert-butyl-4-hydroxy-5-methylphenyl)- dicyclopentadien, Bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert- butyl-4-methylphenyl]terephthalat, l,l-Bis-(3,5-dimethyl-2-hydroxyphenyl)- butan, 2,2-Bis(3,5-di-tert-butyl-4-hydroxyphenyl)propan, 2,2-Bis-(5-tert-butyl- 4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutan, 1,1,5, 5-Tetra(5-tert- butyl-4-hydroxy-2-methylphenyl)pentan;,

[0119] 0-, N- und S-Benzyl-Verbindungen, wie z.B. 3,5,3',5'-Tetra-tert-butyl-4,4'- dihydroxydibenzylether, Octadecyl-4-hydroxy-3,5-dimethylbenzylmercapto- acetat, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetat, Tris(3,5-di- tert-butyl-4-hydroxybenzyl)amin, , Bis(4-tert-butyl-3-hydroxy-2,6-dimethyl- benzyl)dithioterephthalat, Bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfid, lsooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetat;

[0120] hydroxybenzylierte Malonate, wie z.B. Dioctadecyl-2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonat, Dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl- benzyl)malonat, Didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxy- benzyl)malonat, Bis[4-(l,l,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert- butyl-4-hydroxybenzyl)malonat; aromatische Hydroxybenzylverbindungen, wie z.B. l,3,5-Tris(3,5-di-tert-butyl- 4-hydroxybenzyl)-2,4,6-trimethylbenzol, l,4-Bis(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,3,5,6-tetramethylbenzol, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxy- benzyl)phenol;

[0121] Triazinverbindungen, wie z.B. 2,4-Bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazin, 2-Octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-l,3,5-triazin, 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,2,3-triazin, l,3,5-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurat, 1,3,5- Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurat, 2,4,6-Tris(3,5-di- tert-butyl-4-hydroxphenylethyl)-l,3,5-triazin, l,3,5-Tris(3,5-di-tert-butyl-4- hydroyphenylpropionyl)hexahydro-l,3,5-triazin, l,3,5-Tris(3,5-dicyclohexyl-4- hydroxybenzyl)isocyanurat;

[0122] Benzylphosphonates, such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert- butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;

[0123] acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;

[0124] Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g., methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,

[0125] 3- Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylol- propan, 4-Hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan;

[0126] Ester der ß-(5-tert-Butyl-4-hydroxy-3-methylphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, n-Octanol, i-Octanol, Octadecanol, 1,6-Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol,

[0127] Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3- Thiaundecanol, 3-Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan,

[0128] 4- Hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan, 3,9-Bis[2-{3-(3- tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-l,l-dimethylethyl]-

[0129] 2,4,8,10-tetraoxaspiro[5.5]undecan; Ester der ß-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6- Hexandiol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris- (hydroxyethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3- Thiapentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl- l-phospha-2,6,7-trioxabicyclo[2.2.2]octan;

[0130] Esters of 3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, Pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane;

[0131] Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide; ascorbic acid (vitamin C).

[0132] Particularly favored phenolic antioxidants are the following structures:

[0133] 

[0134]

[0135]

[0136] Suitable phosphites / phosphonites include, for example:

[0137] Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri(nonyl- phenyl)phosphit, Trilaurylphosphite, Trioctadecylphosphit, Distearylpenta- erythritoldiphosphit, Tris-(2,4-di-tert-butylphenyl) phosphit, Diisodecylpenta- erythritoldiphosphit, Bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphit, Bis(2,4-di-cumylphenyl)pentaerythritoldiphosphit, Bis(2,6-di-tert-butyl-4- methylphenyl)pentaerythritoldiphosphit, Diisodecyloxypentaerythritol- diphosphit, Bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphit, Bis(2,4,6-tris(tert-butylphenyl)pentaerythritoldiphosphit, Tristearylsorbitol- triphosphit, Tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylendiphosphonit, 6- lsooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-l,3,2-dioxaphosphocin, Bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphit, Bis(2,4-di-tert-butyl-6- methylphenyl) ethylphosphit, 6-Fluoro-2,4,8,10-tetra-tert-butyl-12-methyl- dibenz[d,g]-l,3,2-dioxaphosphocin, 2,2'2"-Nitrilo[triethyltris(3,3",5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert- butylphenoxy)-1,3,2-dioxaphosphiran.,

[0138] Other suitable phosphites are the commercial products Weston 705 (manufacturer: Addivant) and Doverphos LGP 11 (manufacturer: Dover Chemical Corporation), which are liquid phosphites.

[0139] Particularly favored phosphites / phosphonites are:

[0140]

[0141] 

[0142]

[0143] , where n > 1

[0144] Suitable amine antioxidants include, for example:

[0145] N,N'-Di-isopropyl-p-phenylendiamin, N,N'-Di-sec-butyl-p-phenylendiamin, N,N'-Bis(l,4-dimethylpentyl)-p-phenylendiamin, N,N'-Bis(l-ethyl-3-methyl- pentyl)-p-phenylendiamin, N,N'-Bis(l-methylheptyl)-p-phenylendiamin, N,N'-Dicyclohexyl-p-phenylendiamin, N,N'-Diphenyl-p-phenylendiamin, Ν,Ν'- Bis(2-naphthyl)-p-phenylendiamin, N-lsopropyl-N'-phenyl-p-phenylendiamin, N-(l,3-Dimethylbutyl)-N'-phenyl-p-phenylen-diamin, N-(1-Methylheptyl)-N'- phenyl-p-phenylendiamin, N-Cyclohexyl-N'-phenyl-p-phenylendiamin, 4-(p- Toluolsulfamoyl)diphenylamin, N,N'-Dimethyl-N,N'-di-5ec-butyl-p-phenylen- diamin, Diphenylamin, N-Allyldiphenylamin, 4-lsopropoxydiphenylamin, N- Phenyl-l-naphthylamin, N-(4-tert-Octylphenyl)-l-naphthylamin, N-Phenyl-2- naphthylamin, octyliertes Diphenylamin, z.B. p,p'-Di-tert-octyldiphenylamin, 4-n-Butylaminophenol, 4-Butyrylaminophenol, 4-Nonanoylaminophenol, 4- Dodecanoylaminophenol, 4-Octadecanoylamino-phenol, Bis(4-methoxy- phenyl)amin, 2,6-Di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-Diaminodiphenylmethane, 4,4'-Diaminodiphenylmethane, N,N,N',N'-Tetra-methyl-4,4'-diaminodiphenylmethane, 1,2-Bis[(2-methylphenyl)amino]ethane, 1,2-Bis(phenylamino)propane, (o-Tolyl)biguanide, Bis[4-(1',3'-dimethylbutyl)phenyl]amine, ieri-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated ieri-butyl / ieri-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, a mixture from mono- and dialkylated te / t-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated te / t-butyl / te / t-octylphenothiazines, a mixture of mono- and dialkylated ieri-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, and mixtures or combinations thereof.

[0146] Other suitable amine antioxidants are hydroxylamines or N-oxides (nitrons), such as N,N-dialkylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α-hexadecylnitrone, and Genox EP (addivant) according to the formula: R, , R s - C 14 - C 24 Alkyl

[0147]

[0148] Genox EP

[0149] Other suitable stabilizers are thiosynergists. Suitable thiosynergists include, for example, distearylthiodipropionate, dilaurylthiodipropionate, or the compound according to the following formula:

[0150]

[0151] Other suitable stabilizers, especially for polyamides, are copper salts such as copper(I) iodide, copper(I) bromide, or copper complexes such as triphenylphosphine-copper(I) complexes.

[0152] Suitable hindered amines include, for example, l,l-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebazate, bis(l-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, bis(l,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4- ieri-Octylamino-2,6-dichloro-l,3,5-triazine, Tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-l,2,3,4-butanetetracarboxylate, l,l'-(l,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-l,3,5-triazine, the reaction product of 7,7,9,9-,

[0153] Tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin.

[0154] Preferred hindered amines continue to exhibit the following structures:

[0155]

[0156] 33

[0157] Preferred oligomeric and polymeric hindered amines exhibit the following structures:

[0158]

[0159]

[0160] Suitable lactones include, for example: 5,7-di-tert-butyl-3-(3,4-dimethyl-phenyl)-3H-benzofuran-2-one, 5,7-di-tert-butyl-3-[-4-(2-stearoyloxyethoxy)-phenyl]-benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-οη), as well as phosphorus-containing 3-phenylbenzofuran-2ones.

[0161] Suitable metal deactivators include, for example, N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl)oxylyldihydrazide, and N,N'-bis(salicyloyl)thiopropionyldihydrazide.

[0162] Suitable dispersing agents include, for example:

[0163] Polyacrylates, e.g., copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g., N,N'-1,2-ethanediylbisoctadecanamide, sorbitan esters, e.g., monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, e.g., polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride polysiloxanes: e.g., dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g., polyethylene block-polyethylene oxide, dendrimers, e.g., dendrimers containing hydroxyl groups.

[0164] Suitable nucleating agents include, for example, talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as benzoic acid, succinic acid, adipic acid, sodium benzoate, zinc glycerolate, aluminum hydroxy-bis(4-te / t-butyl)benzoate, benzylidene sorbitols such as 1,3:2,4-bis(benzylidene)sorbitol or 1,3:2,4-bis(4-methylbenzylidene)sorbitol, 2,2 ' - Methylene bis-(4,6-di-te / t-butylphenyl)phosphate, as well as triamides and diamides such as trimesic acid tricyclohexylamide, trimesic acid tri(4-methylcyclohexylamide), trimesic acid tri(tert-butylamide), N,N ' ,N " -1,3,5-

[0165] Benzenetriyltris(2,2-dimethyl-propanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide.

[0166] Suitable antinuclear agents include, for example, azine dyes such as nigrosine, ionic liquids and / or lithium salts.

[0167] Suitable flame retardants include, for example:

[0168] a) Inorganic flame retardants such as Al(OH)3, Mg(OH)2,

[0169] AIO(OH), MgCO3, layered silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts, such as

[0170] Mg-Al silicates, POSS (polyhedral oligomeric silsesquioxane) compounds, huntite, hydromagnesite or halloysite, as well as Sb2O3, Sb2O5, MoO3, zinc stannate, zinc hydroxystannate,

[0171] b) Nitrogen-containing flame retardants such as melamine, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantoin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium phosphate, as well as the corresponding pyrophosphates and polyphosphates, poly-[2,4-(piperazine-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide,

[0172] c) Radical initiators, such as alkoxyamines, hydroxylamine esters,

[0173] Azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as e.g.

[0174] Hydroxyimide esters or hydroxyimide ethers

[0175] d) Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as alkyl phosphinate salts, e.g. diethyl phosphinate-aluminum or diethyl phosphinate-zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,

[0176] e) Halogen-containing flame retardants based on chlorine and bromine, such as polybrominated diphenyl oxides, e.g., decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromneopentyl)phosphate, tetrabromophthalic acid, 1,2-bis(tribromphenoxy)ethane, hexabromocyclododecane, brominated diphenylethane, tris(2,3-dibromopropyl)isocyanurate, ethylene bis(tetrabromophthalimide), tetrabromobisphenol A, brominated

[0177] Polystyrene, brominated polybutadiene or polystyrene-brominated polybutadiene copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabrombenzyl acrylate, possibly in combination with Sb203 and / or Sb205,

[0178] f) Borates such as zinc borate or calcium borate, possibly on a support material such as silica

[0179] g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzthiazole and sulfenamides, h) Anti-drip agents such as polytetrafluoroethylene,

[0180] i) Silicon-containing compounds such as polyphenylsiloxanes, j) Carbon modifications such as carbon nanotubes (CNTs), expandable graphite or graphene

[0181] k) as well as combinations or mixtures thereof.

[0182] Suitable fillers and reinforcing materials include synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass beads (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour, or fibers from natural products such as cellulose or synthetic fibers. Other suitable fillers include hydrotalcites or zeolites or layered silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite, and halloysite.

[0183] Suitable pigments can be inorganic or organic. Examples of inorganic pigments are titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, and carbon black; examples of organic pigments are...

[0184] Anthraquinones, Anthanthrone, Benzimidazolone, Quinacridone,

[0185] Diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines, or pyranthrones. Other suitable pigments include metal-based effect pigments or metal oxide-based pearlescent pigments.

[0186] Suitable chain extenders for the linear molecular weight increase of polycondensation polymers such as polyesters or polyamides include, for example, diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyl lactams, bis-maleimides, dicyanates, and (poly)carbodiimides. Other suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl(meth)acrylate copolymers, polystyrene-maleic anhydride copolymers, and polyethylene-maleic anhydride copolymers.

[0187] Suitable optical brighteners include, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls, and in particular optical brighteners of the following formulas:

[0188]

[0189] Suitable filler deactivators include, for example, polysiloxanes,

[0190] Polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl(meth)acrylates and their copolymers, e.g. with styrene, as well as epoxides, e.g. of the following structures:

[0191]

[0192]

[0193] n = 1-10

[0194] Suitable antistatic agents include, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as polyetheramides.

[0195] Suitable antiozonants include the amines mentioned above, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, and N-cyclohexyl-N'-phenyl-p-phenylenediamine. Suitable demolding aids include, for example, montan waxes.

[0196] The incorporation of the stabilizers and / or the additive composition, and optionally the additional additives, into the plastic is carried out using conventional processing methods. The polymer is melted and mixed with the additive composition according to the invention and any further additives, preferably using mixers, kneaders, and extruders. Preferred processing machines include extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, and co-kneaders, preferably equipped with vacuum degassing. The processing can be carried out under air or, optionally, under inert gas conditions, such as...

[0197] Nitrogen is used as a protective gas.

[0198] Furthermore, the additive compositions can be in the form of masterbatches or concentrates, which, for example, contain 20-90% of the additives according to the invention or the additive compositions in a

[0199] Polymers are contained, produced, and introduced. Concentrates consisting of the additive and / or additive composition and a lubricant are also preferred. The lubricant is preferably a salt of a long-chain fatty acid such as calcium stearate, magnesium stearate, or zinc stearate, a polyethylene wax, or a polypropylene wax. These concentrates can then be in the form of compacted, granulated, or extruded product forms.

[0200] Furthermore, it is advantageous if, in addition to the compound according to general formula I, at least one further primary and / or secondary antioxidant, in particular at least one further primary and / or secondary antioxidant selected from the group consisting of phenolic antioxidants, phosphites, phosphonites, amines, hydroxylamines and mixtures or combinations thereof, is used to stabilize the organic materials.

[0201] In the event that the organic materials are plastic compositions or polymer compositions containing the stabilizers according to the invention, these are particularly suitable for further processing into special molded parts, such as injection-molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies,

[0202] Tapes and membranes, such as geomembranes, manufactured by extrusion, injection molding, blow molding, calendering, pressing, spinning, rotomoulding, or coating processes, are used, for example, in the electrical and electronics industry, the construction industry, the transportation industry (automotive, aircraft, ship, rail), for medical applications, for household and electrical appliances, vehicle parts, consumer goods, packaging, furniture, and textiles. These molded parts are also part of the present invention.

[0203] Preferably, the compositions according to the invention consist of 0.01–5.0 wt% of the stabilizers according to general formula I, 0–5.0% of a further additive, and 95–99.99 wt% of a polymer; particularly preferably, 0.02–3 wt% of the stabilizers according to the invention, 0–3.0% of a further additive, and 97–99.98% of a polymer; most preferably, 0.05–2 wt% of the stabilizers according to the invention, 0–2 wt% of a further additive, and 98–99.95 wt% of a polymer. The present invention also relates to an organic material that is to

[0204] For stabilization purposes, the material comprises at least one stabilizer or a mixture of several stabilizers according to general formula I, as defined above. All the aforementioned descriptions of general formula I apply equally to the correspondingly stabilized organic material. In a particularly preferred embodiment, the organic material is a polymer composition, especially with the polymers as described above. Furthermore, the invention relates to a method for stabilizing organic materials.

[0205] Materials, especially plastic compositions, particularly preferably resistant to oxidative, thermal and / or actinic degradation, in which one or more compounds according to general formula I are incorporated into the organic material. The incorporation can be carried out in any manner known from the prior art.

[0206] The present invention also relates to particularly efficient stabilizers, which are characterized in more detail in the following formulas:

[0207] Formula II

[0208] where R 2 to R 5 , R 7 to R 10 , Y and A are defined as above, with the proviso that fragment AX contains a sulfur atom and n = 1

[0209] Formula 111

[0210] where X, n and B are defined as above; and Formula IV

[0211] where A is defined as above.

[0212] The present invention will be explained in more detail by reference to the following examples, without limiting the invention to specific details.

[0213] Synthesis of the new stabilizers:

[0214] The absolute toluene (99.8%), lithium diisopropylamide (LDA), and elemental sulfur (pa, > 99.5%) used for the syntheses were obtained from Sigma Aldrich; phenothiazine (98+%) from Alfa Aesar; acetonitrile, anhydrous diethyl ether, and the 1.6 M (15%) n-butyllithium solution in n-hexane from Merck KGaA; and chlorodiphenylphosphine from BASF. The compound 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (BDBDA) was obtained from TCI Tokyo Kasei, and absolute tetrahydrofuran from Acros Organics. 2-Chloro-5,5-dimethyl-1,3,2-dioxa-phosphorinane (DDP-CI) was synthesized from phosphorus trichloride and 1,3-dimethylpropane-1,3-diol using a method known from the literature.

[0215] Example 1

[0216] Synthesis of phenothiazine-DOP:

[0217]

[0218] DOP-CI Phenothiazine Phenothiazine-DOP

[0219] Into a carefully dried, nitrogen-filled 500 mL three-necked flask equipped with a magnetic stirrer, nitrogen supply, and pressure-equalizing dropping funnel, absolute toluene (150 mL) and 47.3 g of a 2 M lithium diisopropylamide solution in THF (LDA; 0.095 mol) were added via syringe through a septum. Phenothiazine (17.93 g, 0.090 mol) was then added countercurrently under nitrogen. Into the slightly warmed dropping funnel, absolute toluene (120 mL) was added via syringe through a septum, followed by molten DOP-Cl (21.23 g, 0.090 mol) in countercurrent nitrogen. (The bottle containing the DOP-Cl had been previously warmed to approximately 100°C to melt the reagent.) The DOP-Cl solution was added dropwise over 30 minutes at room temperature with stirring. The reaction mixture was then stirred for 1 hour at room temperature. After the solids (mainly lithium chloride) had settled at the bottom of the flask, the mixture was removed.After the residue had separated from the flask wall, the supernatant solution was decanted under inert conditions. 80 mL of absolute toluene were added to the residue via a syringe through a septum. The mixture was stirred for 30 min at 45 °C and, after settling of the solid, decanted. Both solutions were combined, and the toluene was removed under vacuum. The resulting residue was dissolved in 80 mL of dry acetonitrile with heating. Upon cooling, the phenothiazine-DOP precipitated. After storing the tightly sealed flask in a refrigerator (approx. 15 h), the supernatant solution was separated by decantation. Finally, the adhering solvent was removed under vacuum. In this way, phenothiazine-DOP was obtained as a white solid in a yield of 78%. 31 P-NMR (300 MHz, CDCI3, 8) δ = 94.2 ppm. 1 H NMR (300 MHz, CDCI3, 8) δ = 7.86 - 6.77 (m, 16.3H) ppm.

[0220] Example 2

[0221] Synthesis of phenothiazine DOPS:

[0222]

[0223] Phenothiazine-DOP Phenothiazine-DOPS In a carefully dried, nitrogen-filled 250 mL three-necked flask equipped with a magnetic stirrer and nitrogen supply line, 60 mL of absolute toluene were added via syringe through a septum, along with phenothiazine-DOP (4.97 g, 0.013 mol) and elemental sulfur (0.43 g, 0.013 mol) in countercurrent nitrogen. The reaction mixture was stirred first for 3 h at 80 °C, then for 30 min at 90 °C. After removal of the toluene by vacuum distillation, a crystalline solid was obtained. NMR spectroscopy showed that the sulfurization reaction to form phenothiazine-DOPS had proceeded completely.

[0224] 31 P-NMR (300 MHz, CDCI3, 14) δ = 67.4 ppm. 1 H-NMR (300 MHz, CDCI3, 14) δ = 8.11 - 6.95 (m, 17.5H) ppm. Example 3

[0225] Synthesis of phenothiazine PPh2:

[0226]

[0227] Ph,PCI PTZ PTZ PPh,

[0228] Into a carefully dried, nitrogen-filled 250 mL three-necked flask equipped with a magnetic stirrer, dropping funnel, and nitrogen supply line, absolute toluene (40 mL) and LDA (7 mL, 0.014 mol) were added via syringe through a septum, and phenothiazine (2.39 g, 0.012 mol) were added countercurrently with nitrogen. The mixture was heated to approximately 40 °C to dissolve and then cooled in an ice bath. Subsequently, absolute toluene and chlorodiphenylphosphine (2.65 g, 0.012 mol) were added dropwise over 10 minutes via syringe through a septum with nitrogen into a dropping funnel. The reaction mixture was stirred in the ice bath for 1 h. NMR spectroscopy of the reaction solution showed that the desired product had been formed.

[0229] 31P-NMR (300 MHz, CDCI3) δ = 70.3 ppm. 1H-NMR (300 MHz, CDCI3) δ = 7.66 - 6.56 ppm.

[0230] Example 4 Synthesis of Phenothiazine PPh2S:

[0231]

[0232] In a carefully dried, nitrogen-filled 250 mL three-necked flask equipped with a magnetic stirrer, reflux condenser, and nitrogen supply line, absolute toluene (60 mL) and elemental sulfur (0.42 g, 0.013 mol) were added countercurrently to the reaction solution obtained in Exemplar 3 via a syringe through a septum. The reaction mixture was stirred for 3 h at 80 °C and stored overnight in a refrigerator (2 °C). The precipitate was filtered off, the filtrate was concentrated by vacuum distillation to remove the toluene, cooled again, and the precipitate was filtered off once more. The product was then recrystallized from acetonitrile. The yield was 2.74 g (54%). NMR spectroscopy showed that the sulfurization reaction had proceeded to completion, forming phenothiazine PPh₂S.

[0233] 31 P-NMR (300 MHz, CDCI3) δ = 62.6 ppm. 1H NMR (300 MHz, CDCI3) δ = 8.17 - 6.89 ppm.

[0234] Example 5

[0235] Synthesis of phenothiazine-DDP:

[0236]

[0237] DDP-CI Phenothiazine Phenothiazine-DDP

[0238] In a carefully dried and argon-filled 100 mL three-necked flask equipped with a magnetic stirrer, septum, and argon supply line, absolute THF (40 mL) and phenothiazine (2.99 g, 0.015 mol) were added. Then, 9.4 mL of a 15% solution of n-butyllithium in n-hexane (0.015 mol) was added through the septum via a syringe while stirring. After stirring the flask contents for 20 min, 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphorinane (DDP-Cl, 2.52 g, 0.015 mol) was added dropwise through the septum via a syringe over 10 minutes. The reaction mixture was stirred for 2 h at room temperature. NMR spectroscopy of the reaction solution showed the formation of phenothiazine-DDP.

[0239] 3 1 P-NMR (300 MHz, CDCI3) δ = 127.0 ppm.

[0240] Example 6

[0241] Synthesis of phenothiazine-DDPS:

[0242]

[0243] Elemental sulfur (0.48 g, 0.015 mol) was added countercurrently with argon to the solution of phenothiazine-DDP in THF obtained in embodiment 5. The mixture was then stirred for 3 h at 50 °C. Afterwards, the solvent was removed in the

[0244] Vacuum was removed, and the residue was recrystallized from acetonitrile. The yield of spectroscopically pure phenothiazine-DDPS was 85%.

[0245] 31 P-NMR (300 MHz, CDCI3) δ = 56.1 ppm. X H-NMR (300 MHz, CDCI3) δ = 7.94 - 7.14 (m, 8.5 H, Ar), 3.83 - 3.57 (m, 4 H, CH2), 1.23 (s, 3 H, CH3), 0.76 (s, 3 H,

[0246] CH3) ppm. 13 C-NMR (300 MHz, CDCI3) δ = (140.0, 130.1, 127.7, 127.5, 125.9, 123.7, 77.0, 32.1, 22.1, 21.1) ppm

[0247] Melting point (°C): 205

[0248] Example 7

[0249] Synthesis of BDBDA-DOP:

[0250]

[0251] The apparatus used was carefully dried. The synthesis was carried out under a nitrogen atmosphere.

[0252] 4.5 g (0.011 mol) of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (BDBDA) were placed in a 250 mL three-necked flask equipped with a magnetic stirrer, dropping funnel, and argon supply line. The mixture was then heated in an oil bath (85°C) for approximately 30 min at approximately 0.02 mbar. After cooling to room temperature and filling the flask with nitrogen, 50 mL of dry toluene were added via syringe. Subsequently, 6.9 mL of a 15% solution of n-butyllithium in n-hexane (0.011 mol) were added via syringe over a period of 10 min. The reaction mixture was heated to approximately 40°C and then cooled in an ice bath. Finally, a solution of 2.6 g (0.011 mol) of DOP-Cl in abs. Toluene (30 ml) was added dropwise over 10 minutes. The reaction mixture was then stirred at room temperature for 1 hour. Subsequently, the lithium chloride was filtered off under inert conditions. The resulting BDBDA-DOP solution was used for embodiment 9.

[0253] 31P-NMR (300 MHz, CDCI3) δ = 79.9 ppm. Example 8

[0254] Synthesis of BDBDA-DOPS:

[0255]

[0256] Elemental sulfur (0.45 g, 0.014 mol) was added to the BDBDA-DOP solution in toluene obtained in embodiment 7. The mixture was then stirred for 3 h at 80 °C. The solvent was then removed under vacuum. The resulting residue was recrystallized twice from acetonitrile.

[0257] The yield of spectroscopically pure BDBDA-DOPS was 73%.

[0258] 31 P-NMR (300 MHz, CDCI3) δ = 66.0 ppm.

[0259] Example 9

[0260] Synthesis of BDBDA-DPhP:

[0261]

[0262] The apparatus used was carefully dried. The synthesis was carried out under a nitrogen atmosphere.

[0263] In a 250 mL three-necked flask equipped with a magnetic stirrer, dropping funnel, and argon supply line, 6.1 g (0.015 mol) of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (BDBDA) were added. The mixture was then heated in an oil bath (85°C) for approximately 30 min at approximately 0.02 mbar. After cooling to room temperature and filling the flask with nitrogen, 50 mL of dry toluene were added via syringe. Subsequently, 9.4 mL of a 15% solution of n-butyllithium in n-hexane (0.015 mol) were added via syringe over 10 min. The reaction mixture was stirred for 30 min. Then, a solution of 3.3 g (0.015 mol) of DPhP-Cl in absolute toluene (30 mL) was added dropwise over 10 min. The reaction mixture was then stirred for 3 hours at room temperature. The lithium chloride was then filtered off under inert conditions. The resulting BDBDA-DPhP solution was used for embodiment 10.

[0264] 31P-NMR (300 MHz, CDCI3) δ = 54.9 ppm. Example 10

[0265] Synthesis of BDBDA-DPhPS:

[0266]

[0267] Elemental sulfur (0.58 g, 0.018 mol) was added to the solution of BDBDA-DPhP in toluene obtained in embodiment 9. The mixture was then stirred for 3 h at 60 °C. The solvent was then removed under vacuum. The residue thus obtained was recrystallized twice from acetonitrile. The yield of spectroscopically pure BDBDA-DPhPS was 78% (based on

[0268] DPhP-CI).

[0269] 31 P-NMR (300 MHz, CDCI3) δ = 62.3 ppm.

[0270]

[0271] 206.8 g of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine (BDBDA) were placed in a carefully dried, argon-filled, two-liter, three-necked flask equipped with a magnetic stirrer, dropping funnel, and argon supply line. The flask was then heated in an oil bath (85°C) for approximately 30 minutes at approximately 0.02 mbar. After cooling to room temperature and filling the flask with nitrogen, 500 ml of dry THF were added via syringe. A colorless solution was obtained. Over the course of approximately 60 minutes, approximately 323 ml of a 1.6 molar solution of n-butyllithium in n-hexane were added dropwise (via syringe) while stirring. The flask was cooled in a water bath during this process. A yellow solution was obtained, which was stirred for 30 minutes.

[0272] Then, approximately 84.3 g of DDP-Cl were added dropwise via syringe over about 90 minutes while stirring (the flask remained in the water bath). As the reagent was added, the yellow color faded, and after about two-thirds of the DDP-Cl had been added, the reaction mixture became cloudy. Then, 100 ml of dry n-hexane were added while stirring to precipitate any remaining dissolved LiCl. Stirring continued for several minutes. The flask containing the product solution was stored overnight at room temperature under nitrogen. The precipitated LiCl was removed by decantation under inert conditions. Most of the volatile components of the solution were then distilled into a cold trap, with the pressure slowly reduced to approximately 50 mbar and the temperature of the oil bath increased to 60°C. A viscous, oily residue was obtained, which was further heated to approximately 70°C. Approximately 800 ml of acetonitrile was added to this through a funnel.

[0273] The contents of the flask were then heated under a nitrogen atmosphere until just below the boiling point. A cloudiness remained, which settled after the stirrer was stopped. After the contents of the flask had cooled, under

[0274] Under inert conditions, the product was decanted into a 2-liter flask filled with nitrogen. The remaining residue was mixed with approximately 100 ml of acetonitrile, heated, and filtered through a paper filter (into the 2-liter flask containing the decanted solution). Upon cooling, crystalline product precipitated from the combined product solution onto the flask wall. After approximately 2 hours, when significant amounts of the product had already crystallized, the flask was transferred to a refrigerator and stored there overnight. The supernatant solution was then separated by decantation. The crude product thus obtained was extracted from 750 ml of acetonitrile under a nitrogen atmosphere.

[0275] The product was recrystallized. It was collected using a porcelain funnel / filter paper siphon (in the presence of air) and subsequently dried in a flask using a diaphragm pump under vacuum, with gentle heating using a hairdryer and frequent agitation. A white powder (201 g) was obtained. An additional 10 g of the product was isolated from the residual recrystallization solution. NMR spectroscopy of the product showed a purity of > 99.5%.

[0276] 31 P-NMR (300 MHz, CDCI3) δ = 121.0 ppm; 1 H-NMR (300 MHz, CDCI3) δ = 7.10 - 7.33 (m, 18 H, Ar), 3.53 - 3.56 (d, 4 H, CH2), 1.72 (s, 12 H, H3C-C-CH3), 1.04 (s, 3 H, CH3) , 0.61 (s, 3 H, CH3) ppm. 13 C-NMR (300 MHz, CDCI3, chromium acetylacetonate) δ = 140.0 (s, 2C), 146.2 (s, 2C), 142.7 (d, 2C), 128.0 (s, 4C), 127.4 (s, 4C), 126.8 (s, 4C), 125.6 (s, 2C), 124.8 (d, 4C), 72.0 (s, 2C), 42.6 (s, 2C),

[0277] 32.3 (d, IC), 30.8 (s, 4C), 22.4 (d, 2C) ppm.

[0278] Melting point (°C): 98-99°C Example 12

[0279] Synthesis of BDBDA-DDPS:

[0280]

[0281] The apparatus used was carefully dried.

[0282] BDBDA (239.7 g) was added, then the apparatus was evacuated three times and refilled with nitrogen to remove any remaining moisture. Subsequently, 440 ml of dry THF were added via syringe. A colorless solution was obtained. Over approximately 70 minutes, 375 ml of a 1.6 molar butyllithium solution in n-hexane were added dropwise (via syringe) while stirring. The flask was cooled in a water bath during this process. A yellow solution was obtained, which was stirred for another 30 minutes. Then, over approximately 80 minutes, 97.8 g of DDP-CI were added dropwise via syringe while stirring (flask still in the water bath), resulting in a pale yellow suspension. A 31P-NMR spectrum of this suspension recorded (CDCI3) that showed complete conversion of the DDP-CI.

[0283] The reaction mixture was stored overnight at room temperature under nitrogen.

[0284] The precipitated LiCl was separated by decantation under inert conditions. The solution was transferred to a 2 L flask. 20 mL of THF and 50 mL of cyclohexane were added to the salt residue (to largely dissolve any remaining product). The mixture was then stirred and filtered through a paper filter (into the 2 L flask containing the BDBDA-DDP solution). The combined solution was light brown and was subsequently subjected to the sulfurization reaction.

[0285] The 2-liter flask was equipped with an internal thermometer. Approximately 20 g of sulfur were then added in four portions over about 15 minutes while stirring, with the flask immersed in an oil bath. A significant temperature increase to approximately 45°C was observed. Once the temperature had passed its maximum, the oil bath was heated to 57°C over 30 minutes. Stirring continued for another 30 minutes at an internal temperature of approximately 50-52°C, after which an NMR sample was taken. 31 The P-NMR spectrum of the product solution showed that the

[0286] Sulfuring had been carried out with very high selectivity.

[0287] The resulting solution was transferred to a 2-liter single-necked flask. It was rinsed with 40 ml of warm THF, as a small amount of product had already crystallized at the bottom of the three-necked flask. Further product precipitated at the bottom of the single-necked flask. To ensure a sufficiently complete precipitation,

[0288] To achieve crystallization of the product, approximately half of the solvents THF and n-hexane were distilled using a rotary evaporator (water bath: 40°C). The pressure was reduced in small increments. During distillation, a significant portion of the product crystallized. The sealed flask was stored overnight in a refrigerator (approx. 5°C).

[0289] The crystallized product was filtered off. A beige-colored crystalline solid was obtained, the 31The 31P NMR and proton spectra already showed good purity (approximately 99 mol% purity in the phosphorus spectrum; the proton spectrum also showed hardly any impurities). Approximately 230 g of the substance were obtained. The remaining solution was washed with water to remove the remaining LiCl (the aqueous phase was brown and was discarded). It was then strongly concentrated on a rotary evaporator under partial vacuum, yielding another product fraction. Further purification was carried out by recrystallization from acetonitrile and drying under vacuum with gentle heating. A total of 256 g of pure BDBDA-DDPS was obtained as a white solid (77% of the theoretical amount).

[0290] 31 P-NMR (300 MHz, CDCI3) δ = 64.1 ppm; X H-NMR (300 MHz, CDCI3) δ = 7.15-7.35 (m, 18 H, Ar), 4.28-4.36 (q, 2H, CH2), 3.69-3.82 (q, 2H, CH2), 1.68 (s, 12 H, H3C-C-CH3), 0.87 (s, 3 H, CH3) , 0.67 (s, 3 H, CH3) ppm.

[0291] Melting point (°C): 133-135 Example 13

[0292] Synthesis of BDBDA-DDP from PCI3, BDBDA and 1,3-dimethylpropane-1,3-diol:

[0293]

[0294] The apparatus used was carefully dried. The synthesis was carried out under a nitrogen atmosphere.

[0295] BDBDA (11.4 g) was introduced, then the apparatus was evacuated three times and refilled with nitrogen to remove any moisture adhering to the BDBDA powder. Subsequently, 100 ml of absolute

[0296] Diethyl ether was added via syringe. The resulting solution was cooled to approximately 10°C. Then, 2.8 g of triethylamine and 3.84 g of [unclear text] were added.

[0297] Phosphorus trichloride was added successively with stirring, causing a colorless solid to precipitate (triethylammonium chloride). The mixture was stirred for three hours at room temperature. The triethylammonium chloride was then filtered off under inert conditions. The solution was subsequently concentrated under partial vacuum. 31 P-NMR spectrum recorded, which contained only the phosphorus signal of BDBDA-PCI2 (300 MHz, CDCI3; δ =

[0298] 148.8 ppm).

[0299] Then, 6 g of triethylamine and 6 g of 1,3-dimethylpropane-1,3-diol were added. After stirring the reaction mixture for two hours at room temperature, 50 ml of diethyl ether were added. The precipitated triethylammonium chloride was then filtered off, and the solvent was distilled off. The remaining residue was dissolved in acetonitrile.

[0300] recrystallized.

[0301] The yield of spectroscopically pure BDBDA-DDP was 10.9 g (72% of the theoretical amount, based on BDBDA).

[0302] P-NMR (300 MHz, CDCI3) δ = 121.0 ppm; X H-NMR (300 MHz, CDCI3) δ = 7.10 - 7.33 (m, 18 H, Ar), 3.53 - 3.56 (d, 4 H, CH2), 1.72 (s, 12 H, H3C-C-CH3), 1.04 (s, 3 H, CH3) , 0.61 (s, 3 H, CH3) ppm.

[0303] Example 14

[0304] Synthesis of PhP(BDBDA)2

[0305]

[0306] The apparatus used was carefully dried. The synthesis was carried out under a nitrogen atmosphere.

[0307] BDBDA (116.4 g) was added, then the apparatus was evacuated three times and refilled with nitrogen to remove any remaining moisture. Subsequently, 750 ml of dry diethyl ether was added via syringe. A colorless solution was obtained. Over the course of one hour, 171.3 ml of a 1.6 molar butyllithium solution in n-hexane was added dropwise via syringe while stirring and cooling in an ice-water bath. A pale yellow solution of the lithium salt of BDBDA was obtained. Stirring continued for 45 minutes, and then 24.52 g of PhP-Cl₂ were added dropwise via syringe over 20 minutes while stirring to the still-cooled solution. Initially, turbidity developed due to the precipitation of LiCl. Towards the end of the reagent addition, a large amount of product precipitated. Stirring was continued for another hour at a moderate speed. 31P-NMR spectrum of this suspension recorded (CDCI3) showed complete conversion of PhP-CI2 and highly selective product formation.

[0308] The majority of the volatile components were then distilled under a slight vacuum into a receiving flask cooled with liquid nitrogen (the flask was immersed in a water bath of approximately 20°C). Stirring was no longer possible towards the end of the distillation. A stronger vacuum was then briefly applied. 500 ml of absolute toluene (the tip) was added to the resulting residue. The mixture was then heated to approximately 65°C with gentle stirring, at which point the product dissolved, leaving only the LiCl (liquid chlorine) undissolved. This was filtered off under inert conditions. The toluene was then distilled under partial vacuum into a receiving flask cooled with liquid nitrogen (the flask was immersed in an oil bath, initially at approximately 55°C, which was increased to approximately 75°C towards the end of the distillation). Once the toluene had been almost completely distilled, the residue solidified.The resulting solid was stirred for one hour with 1 liter of acetonitrile under reflux and a nitrogen atmosphere. The product was collected using a porcelain funnel / filter paper (in the presence of air). A white crystalline substance was obtained.

[0309] A filter cake was obtained, which was dried under vacuum with moderate heating. The yield of PhP(BDBDA)2 was 112 g (approximately 89% of the theoretically possible amount).

[0310] = 86.0 ppm; 1 H NMR (300 MHz, CDCI3) δ = 7.10- (d, 8H, Ar), 6.78-6.84 (d, 8H, Ar), 1.66 (s; 24 H, H3C-C-CH3) ppm.

[0311] Melting point (°C): 116-118

[0312] Investigations into the Stabilizer Effect in Polypropylene: The experiments on the stabilizer effect with polypropylene were carried out at 230 °C in a twin-screw microextruder. Polypropylene types MOPLEN HP556E and MOPLEN HP500N (products of LyondellBasell Industries) were used, which had previously been milled at 10,000 rpm using a centrifugal mill and dried for approximately 5 hours at 100 °C in a vacuum drying oven (20 mbar). Three extrusion trials were performed for each polymer-additive mixture. The total amount of polymer-additive mixture used in each trial was 4 g. Forces were recorded at one-second intervals during each run using software.

[0313] Tables 1 and 2 list the additives used, their concentrations, and the forces acting at different extrusion times (each as average values ​​from three individual tests). For comparison, extrusions were also carried out with the established stabilizer system ADK-STAB A611 / Caesit AV, as well as pure MOPLEN HP556E and MOPLEN HP5.

[0314] Table 1 (Tests with MOPLEN HP 556E)

[0315]

[0316] Table 2 (Tests with MOPLEN HP 500N)

[0317] Additive force after force after force after force after force after force after

[0318] 30s 60s 120s 180s 300s 600s

[0319] (N) (N) (N) (N) (N) (N)

[0320] - 550 530 510 480 460 450

[0321] Ceasite 0.2% 640 600 580 560 540 520

[0322] ADK-STAB A611

[0323] 0.2% 610 570 560 540 520 530

[0324] PhP(BDBDA)2

[0325] 0.2% 730 730 750 740 740 730

[0326] Ceasit AV 0.2%

[0327] BDBDA-DDP

[0328] 0.2% 600 600 610 600 590 580 Multiple extrusions

[0329] For the extrusions, polypropylene type Moplen HP556E LOI 033L30 from LyondellBasell was used. The tests were carried out on a Thermo Scientific Process 11 twin-screw extruder with a screw diameter of 11 mm.

[0330] In a twin-screw extruder, a total of 350 g each of pure polypropylene, polypropylene, and polypropylene with an additive of 0.3% phenothiazine DOPS (PTZ DOPS) were extruded three times. After each extrusion, the sample was dried for approximately 1 hour in a vacuum drying oven at 60 °C. 50 g were then reserved, and the remaining granules were extruded again. The temperature profile used is shown in Table 3, and the parameters obtained for each extrusion are listed in Tables 4 to 6.

[0331] Table 3: Temperature profile used for extrusions on the twin-screw extruder.

[0332] Table 4: Parameters of the three extrusions of pure polypropylene.

[0333]

[0334] Table 5: Parameters of the three extrusions of polypropylene with an addition of 0.3% phenothiazine DOPS.

[0335] Pure PP 1. Extrusion 2. Extrusion 3. Extrusion

[0336] Engine speed / rpm 150 150 150

[0337] Throughput / g / h 468 576 552

[0338] Melting point / °C 213-215 214-217 214-217

[0339] Melting pressure / bar 27-29 32-33 30-32

[0340] Torque / % 28-30 37-40 33-37

[0341] Torque / Nm 3.4-3.6 4.4-4.8 3.9-4.4

[0342] Torque / kW 0.05 0.06-0.07 0.06-0.07 Subsequently, melt flow measurements were performed on all samples obtained, which had previously been dried overnight in a vacuum drying oven at approximately 60 °C. For this purpose, 3.5 g of each sample were measured at 230 °C and a weight of 2.16 kg (DIN EN ISO 19069). Each sample was measured two to three times, and the results were then averaged. According to the manufacturer, the MVR of the pure polymer should be 1.10 cm. 3 / 10 min. Table 5 shows the results of these measurements.

[0343] Table 6: List of the average MVR values ​​of the three extrusions of pure

[0344] Polypropylene, as well as polypropylene with an addition of 0.3% phenothiazine DOPS.

[0345]

[0346] The comparison of the results in Table 5 shows the very good stabilizing effect of the stabilizers according to the invention, since, in contrast to pure PP, no or only a slight reduction in molecular weight (= higher MVR) takes place.

[0347] Stabilizing effect of the substances according to the invention:

[0348] The phosphorus-containing phenothiazine derivatives according to the invention were tested for their effectiveness as processing stabilizers. The influence of the new additives on the melt viscosity of polypropylene during the extrusion process (230°C) was investigated. During the tests, the force in the extruder was measured as a function of time. The measured force is proportional to the applied torque, and the latter is directly dependent on the melt viscosity. A decrease in the measured force thus indicates polymer degradation during the extrusion process. For comparison, the established stabilizer system AD K-STAB A611 (0.2%) / Caesit AV (0.1%) was tested. Comparative tests with pure polypropylene were also carried out. As expected, a continuous decrease in force was observed with pure polypropylene during the extrusion process. After 10 minutes, the measured force was only about two-thirds of the value measured after 30 seconds.When using the established stabilizer mixture, the strength initially remained constant, as expected, but dropped significantly after only 3 minutes of extrusion and, after 10 minutes of residence time, fell to about two-thirds of the initial value, similar to pure PP. This means that the comparison system loses its effectiveness after a relatively short extrusion time.

[0349] Surprisingly, no change in force was observed during extrusion of polypropylene to which small amounts of the stabilizers according to the invention had been added. Even after a long residence time in the extruder (e.g., 10 minutes!), no decrease in force occurred, while the comparison system had long since lost its effect (sharp drop in the measured force).

[0350] Thus, the stabilizers according to the invention showed excellent and much higher effectiveness compared to the comparison system.

[0351] The tests showed that when using the stabilizers according to the invention, processing of polypropylene in the melt (extrusion, injection molding, etc.) is possible without degradation processes.

[0352] The primary or secondary antioxidant can be incorporated into the organic material in the same way as the compound according to general formula I.

[0353] Primary antioxidants act via a radical mechanism with chain-breaking properties. Secondary antioxidants have a stabilizing effect based on an ionic mechanism and act as hydroperoxide decomposers. A combination of both groups can be used to achieve synergistic effects.

Claims

Patent claims Use of a compound or mixtures of several compounds according to general formula I Formula 1 where Fragment A has the following meaning each independently of each other X is a sulfur atom n is 0 or 1, x 0 or 1 is, Z 1 and Z 2 are selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, heterocyclic groups, wherein one or more further fragments A and / or B may be bonded to the aforementioned groups, as well as a group -OZ 3 , where Z 3 selected from alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, and heterocyclic groups, as well as a group -SZ 4 , where Z 4selected from alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, and heterocyclic groups, where, in the case of x = 1, the remainders Z 1 and Z 2 together with the phosphorus atom they can form a ring system to which one or more further fragments A and / or B may be bonded, fragment B has the following meaning each independently of each other R 1 to R 10 are selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and heterocyclic groups, wherein the groups R 1 and R 6 can also be connected via a grouping -Y- connecting the phenyl groups, where Y is selected from the group consisting of S, O, NH, PH and a covalent bond, wherein fragments A and B are connected to each other by covalent bonding of the phosphorus and nitrogen atoms, and whereby y 1 or 2 is, where x + y = 2, for stabilizing organic materials, especially against oxidative, thermal and / or actinic degradation.

2. Use according to claim 1 for stabilizing plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, gear oils, metalworking fluids, chemicals or monomers.

3. Use according to one of the preceding claims, characterized in that fragment A is selected from the following residues where x = y = 1 where x = 0 and y = 2, or where x = y = 1 where x = y = 1 each independently of each other R is selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, and heterocyclic groups. R 12 selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, heterocyclic groups, wherein the aforementioned groups may also have heteroatoms and / or one or more further fragments A and / or B may be bonded to the aforementioned groups, and X and n as defined in claim 1.

4. Use according to one of the preceding claims, characterized in that fragment A is selected from the following residues where x = 0 and y = 2 in each case, and where x = y = 1 in each case. Use according to one of the preceding claims, characterized in that the compound is defined below according to the general formula I w. where X, n and B are defined as in claim 1.

6. Use according to any of the preceding claims, characterized in that fragment B is selected from the group consisting of the following residues where y = 1 or 2, where y = 1 or 2, as well as where y = 1 or 2 where each is independent of each other R 2 to R 5 and R 7 to R 10 and Y as defined in claim 1.

7. Use according to any of the preceding claims, characterized in that fragment B is selected from the group consisting of the following residues Use according to one of the preceding claims, characterized in that the compound according to general formula I is selected from the group consisting of the following compounds 70 71 72 each independently of each other R 11 selected from the group consisting of hydrogen, alkyl groups, aryl groups, alkylaryl groups, arylalkyl groups and heterocyclic groups. Use according to one of the preceding claims, characterized in that the compound according to general formula I or, in the case of a mixture of several compounds according to general formula I, the entirety of all compounds according to general formula I is contained in the organic material to a weight fraction of 0.01 to 10 wt.%, preferably 0.05 to 5 wt.%, particularly preferably 0.1 to 1.5 wt.%. Use according to any of the preceding claims, for stabilizing plastics, wherein the plastic is selected from the group consisting of a) Polymers made from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methylpentene-1, Polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene acrylates such as ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers), as well as terpolymers such as ethylene-acrylic acid-glycidyl(meth)acrylate, graft polymers such as polypropylene-graft-maleic anhydride, polypropylene-graft-acrylic acid, polyethylene-graft-acrylic acid, polyethylene-polybutylacrylate-graft-maleic anhydride, and blends thereof, b) polystyrene, polymethylstyrene, poly-alpha-methylstyrene, Polyvinylnaphthalene, polyvinylbiphenyl, polyvinyltoluene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-isoprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene acrylonitrile (SAN), styrene-acrylonitrile acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as styrene on butadiene, Maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), and hydrogenated polystyrene derivatives, c) halogen-containing polymers such as polyvinyl chloride (PVC), polychloroprene and polyvinylidene chloride (PVDC), copolymers of vinyl chloride and vinylidene chloride or of vinyl chloride and vinyl acetate, chlorinated polyethylene, polyvinylidene fluoride, epichlorohydrin homo, and copolymers thereof, d) Polymers of unsaturated esters such as polyacrylates and Polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate, polyglycidyl methacrylate, polyacrylonitrile, polyacrylamides, Copolymers such as polyacrylonitrile-polyalkylacrylate, e) Polymers made from unsaturated alcohols and derivatives, such as Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine, f) Polyacetals, such as polyoxymethylene (POM) or copolymers with, for example, butanal, g) Polyphenylene oxides and blends with polystyrene or polyamides, h) Polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide, Po lytet ra hyd rof u ra n, i) Polyurethanes, consisting of hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes (TPU), polyureas, j) Polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 10.10, 10.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, e.g. produced from Terephthalic acid and / or isophthalic acid and aliphatic diamide- nen or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3- Diaminobenzene, blends of different polyamides such as PA-6 and PA 6.6 or blends of polyamides and polyolefins such as PA / PP k) Polyimides, polyamide-imides, polyetherimides, polyesterimides, poly(ether)ketones, polysulfones, polyethersulfones, Polyarylsulfones, polyphenylene sulfides, polybenzimidazoles, polyhydantoins, I) Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxy carboxylic acids such as e.g. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthylate (PEN), poly- 1.4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polyethylene succinate, polytetran ethylene succinate, polycaprolactone, m) Polycarbonates, polyester carbonates, and blends such as e.g. PC / ABS, PC / PBT, PC / PET / PBT, PC / PA n) Cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate, o) Epoxy resins consisting of di- or polyfunctional epoxy compounds in combination with, for example, hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates or catalytically acting hardeners, p) Phenolic resins such as phenol-formaldehyde resins, urea-formaldehyde resins, melamine-formaldehyde resins, q) unsaturated polyester resins made from unsaturated dicarboxylic acids and diols with vinyl compounds, r) silicones, s) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

11. Use according to any of the preceding claims, characterized in that the plastic contains at least one further additive selected from the group consisting of UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact enhancers, plasticizers, lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, marking agents and antifogging agents.

12. Use according to any of the preceding claims, wherein, in addition to the compound according to general formula I, at least one further primary and / or secondary antioxidant, in particular at least one further primary and / or secondary antioxidant selected from the group consisting of phenolic antioxidants, phosphites, phosphonites, amines, hydroxylamines and mixtures or combinations thereof, is used to stabilize the organic materials.

13. Organic material, in particular a plastic composition, containing at least one stabilizer or a mixture of several stabilizers according to general formula I Formula 1 where A, B and y are defined as in claim 1.

14. Method for stabilizing organic materials, in particular against oxidative, thermal and / or actinic degradation, in which one or more compounds according to general formula I Formula 1 wherein A, B and y are defined as in claim 1, into the organic Material is incorporated. Compound according to one of the following general formulas II and IV Formula II where R 2 to R 5 , R 7 to R 10 , Y and A as defined in claims 1 and 3, with the proviso that fragment AX contains a sulfur atom and n = 1; wherein X, n and B are defined as in any one of claims 1, 5 or 7; and where A is defined as in any one of claims 1, 3 or 4.