The present invention relates to the use of efficient phosphorhalti-ger substances, in particular on the basis of diphenylamine and heterocvclischer diphenylamine derivatives as stabilizers for organic materials, in particular for plastic materials against oxidative, thermal and / or actinic degradation. Moreover, the present invention relates to an organic material which is stabilized as described above accordingly. The invention further relates to a method for the stabilization of organic materials, as well as specific stabilizers.

obligations Beschich plastics and plastic-based compositions such as are in the processing and the use of auto-oxidation. This results from radical chain cleavage by mechanochemical process or by UV radiation in the presence of sow erstoff to changes in the polymer chain, such as in the molecular weight or the formation of new chemical groups.
The splitting or chemical modification of polymer molecules ver-poor, the mechanical parameters of the plastics and lead to color changes (yellowing) or other undesirable effects. Thermal degradation limits the maximum operating temperature of plastics, and aging restrict the potential service life of plastic articles, which is shortened with increasing temperature.

Therefore, the addition of specific stabilizers such as antioxidants and

Light stabilizers required which delay biodegradation processes and thus have a significant impact on the processability and the scope of use of plastics.

Currently there is great interest in more efficient stabilizers or

Stabilizer systems are exposed, inter alia, because plastics are increasingly being used in applications in which they increased thermal and mechanical stresses (electrical mobility, lightweight construction, high-performance batteries, etc.). Another reason for more Sta-bilisatoren to search is that many substances currently in use do not meet all requirements for example with regard to their compatibility with the polymers to be protected, low migration and the formation of undesirable degradation products.

There are various stabilizer species of which are significant, including the following:

Processing stabilizers slow down the running at high processing temperatures degradation processes.

- long-term thermal stabilizers are used to retard the aging, especially at elevated temperatures.

High temperature stabilizers counteract the degradation, when plastics are subjected to high temperatures (180 ° C and above).

- UV stabilizers retard or prevent the degradation processes initiated by UV light.

The different stabilizers are used in many cases (synergistic) combinations. The task of stabilizers consists among other things resulting in free radicals intercept and disable the resulting exposure to oxygen peroxides and hydroperoxides, as they cause damage to the polymer chain. The effectiveness of the stabilizers or antioxidants is essential for both the processability of plastics as well as for the life of the items that are made from them. They also affect the maximum operating temperature of the plastics or their possible service life at elevated temperatures.

There are numerous chemical compounds as stabilizers / antioxidants available on the market. The major classes of antioxidants are hindered phenols, phosphites or phosphonites, amines, sulfur compounds, hydroxylamines and lactones. As light stabilizers, which are used at the same time as a long-term heat stabilizers, are esp. Sterically hindered amines, so-called. Mention HALS compounds. The UV absorbers are additionally frequently benzotriazoles, benzophenones, hydroxyphenyltriazines used among others.

The special significance of phosphite stabilizers results from their ability peroxides and hydroperoxides off. However, the substances used to date have drawbacks, including in terms of their thermal stability, long-term efficacy, hydrolysis resistance and compatibility, so that an intensive search for new and better stabilizers which are said to have the following advantages:

Increased hydrolytic stability and improved thermal properties

Applicability at particularly high temperatures;

particularly high and long-lasting efficiency;

no undesirable side effects (discoloration, etc.).

For elastomers derivatives of diphenylamine as an environmentally friendly, low toxic stabilizers. The structurally similar, heterocyclic see connection phenothiazine has also a great ability to deactivate free radicals and is of low toxicity. It is used for storage stabilization of acrylates, methacrylates, and other monomers being prevented by scavenging radicals whose spontaneous polymerization, thus acting in a similar manner as plastics stabilizers. Furthermore, phenothiazine is a powerful antioxidant for lubricants. A patent from 1961 (GB 4331, "phenothiazines stabilizers for Polyethylene") involves the use of phenothiazine as a stabilizer for polyethylene.

So far, very few phosphorus-containing phenothiazine derivatives have been described and shown in patents. Phenothiazine derivatives, the phosphorus-containing substituents on the nitrogen atom wear, are mentioned in the following patents: WO2015158692A1 (2016), WO2015158689A1 (2016), CN 101531578A (2009).

In the patent JP2006328100A (Songwon Industrial Co. LTD, 2006) The following compound is mentioned as flame retardants for plastics:

So far, however an effect of this compound and other phosphorus derivatives of phenothiazine to antioxidant stabilization nothing was known terms.

From structurally related carbazole numerous phosphorus derivatives have been described, and in the patent literature various applications such substances are listed, but not as Stabiii- sator for plastics.

Of phosphorus-containing diphenylamine derivatives, which carry at least one carbon atom on the phosphorus atom is a use or testing as a stabilizer for plastics unknown.

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

This object is with regard to the use of specific materials as a stabilizer having the features of patent claim 1 with regard to a specific stabilized organic material with the features of claim 13, regarding a method for stabilization of organic materials with the features of claim 14 as well as in terms of specific stabilizers with the dissolved features of patent claim 15. The respective dependent claims thereby represent advantageous further.

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

A-By

formula I

in which

the fragment A has the following Matters

wherein each independently

X is a sulfur atom,

n is 0 or 1,

x is 0 or 1,

Z 1 and Z 2 are selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, heterocyclic radicals, wherein one or more additional fragments A and / or B may be attached to the previously mentioned radicals,

and a group -O-Z 3 , wherein Z 3 is selected from alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals, and a group -SZ 4 , wherein Z 4 is selected from alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals wherein in the case of x = 1, the radicals Z 1 and Z 2 may form together with the phosphorus atom form a ring system to which one or more additional fragments a and / or B may be bonded,

the fragment B has the following meaning

wherein each independently

R 1 to R 10 are selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals and heterocyclic radicals, wherein (y in the case of = 1 or 2), preferably in the case of y = 1, the radicals R 1 and R 6 may also be connected via a connecting group, the phenyl groups -Y-, wherein Y is selected from the group consisting of S, 0, NH, PH, as well as a covalent bond,

wherein the fragments A and B are linked by covalent binding of the phosphorus and the nitrogen atom,

and wherein

y is 1 or 2,

wherein x + y = 2,

for the stabilization of organic materials, especially against oxidative, thermal and / or actinic degradation.

The compound of general formula I may exist as a separate molecule here, but likewise also to a polymeric backbone, either within the main chain, it is present bound in a side chain.

Preferably, Z 1 and Z 2 selected from the group consisting of hydrogen, alkyl aryl, alkylaryl, arylalkyl, heterocyclic-rule radicals wherein one or more additional fragments A and / or B may be attached to the previously mentioned radicals,

and a group -O-Z 3 , wherein Z 3 is selected, and in the case of x = 1, the radicals Z from alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals 1 and Z 2 may form together with the phosphorus atom form a ring system to which one or more other fragments a and / or B may be attached.

Surprisingly, it was found that the compounds ge-Mäss the general formula I as defined above, a particularly good efficiency, as stabilizers of organic materials have, so that their use is already in a relatively low concentration leads to high rates stabilize.

In particular, the compounds described above for stabilizing plastics, coatings, lubricants, hydraulic fluids, chemicals, monomers are suitable.

In the above-described compounds of the formula I, it is particularly preferred if the fragment A is selected from the following radicals

wherein each independently

R 11 is selected from the group consisting of hydrogen, Al kylresten, aryl radicals, alkylaryl radicals, arylalkyl radicals and heterocyclic radicals,

R 12 is selected from the group consisting of hydrogen, Al kylresten, aryl radicals, alkylaryl radicals, arylalkyl radicals, heterocyclic radicals, where the radicals mentioned above may have also hetero- roatome and / or the above-mentioned radicals A and several other fragments or / or B may be attached, and

X and n are as defined in claim. 1

More preferably, the fragment A is selected from the following radicals

wherein each of x = y = 1,

where in each case x = 0 and y = 2, and

wherein x = y = in each case applies. 1

With respect to the fragment B, it is advantageous if this is selected from the group consisting of the following radicals

wherein y = 1 or 2,

wherein y = 1 or 2, and

wherein y = 1 or 2

in each case independently of one another R 2 to R 5 and R 7 to R 10 and Y are as defined in the claim. 1

Particular preference is in this case when the fragment B is selected from the group consisting of the following radicals

Particularly preferred compounds which may be used for the purposes of the present invention as stabilizers are listed below:





wherein each independently

R 11 is selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals.

Due to low efficiency, in particular a compound according to the following formula

Ph2N-P(OPh)2

preferably by the use according to the present invention except.

The compound of general formula I or in the case of a mixture of several compounds according to general formula I the sum of all compounds according to general formula I are preferably in a weight proportion of from 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt. -%, more preferably from 0.1 to 1.5 wt .-% in the organic material, ie the material which is subject to oxidative, thermal and / or actinic degradation, is added (incorporated) and / or incorporated by mixing. Particularly in the case of plastic compositions, this can for example take place by kneading or extrusion of these materials during thermal processing by melting like. For liquid-Mate rialen, such as oils, the incorporation takes place of the compounds of general formula I by dissolving or

for the case that the compound according to general formula I are used for the stabilization of plastic materials, it is preferable that the plastic is 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-methyl-pentene-l, polybutadiene, polyisoprene such as also natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of random or block structures, such as polypropylene-polyethylene (EP), EPM or EPDM with, for example, 5-ethylidene-2-norbornene as comonomer, ethylene -Vinylacetat (EVA), ethylene-Acrylester, such as ethylene butyl acrylate, ethylene acrylic acid and their salts (ionomers) and 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,Polyethy-len-polybutyl acrylate-graft-maleic anhydride, and blends such as LDPE / LLDPE or long-chain branched polypropylene copolymers are manufactured with alpha-olefins as comonomers, such as with 1-butene, 1-hexene, 1-octene or 1-octadecene

Polystyrol, Polymethylstyrol, Poly-alpha-methylstyrol,

Polyvinylnaphthalene, Polyvinylbiphenyl, polyvinyl toluene, 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, appropriate graft copolymers such as styrene butadiene, maleic anhydride SBS or SEBS, and graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), as well as hydrogenated polystyrene derivatives, such as polyvinyl

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

Polymers of unsaturated esters such as polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyglycidyl acrylate,

Polyglycidylmethacrylat, Polyacrylnitril, Polyacrylamide, Copolymere wie z.B. Polyacrylnitril-Polyalkylacrylat,

Polymers from unsaturated alcohols and derivatives thereof, such as polyvinyl-nylalkohol, polyvinyl acetate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine

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

Polyphenylene oxides, and blends with polystyrene or polyamides,

Polymers of cyclic ethers such as polyethylene glycol, polypropylene glycol, polyethylene oxide, polypropylene oxide,

Polytetrahydrofuran,

Polyurethanes from hydroxyl-terminated polyethers or polyesters and aromatic or aliphatic isocyanates such as 2,4- or 2,6 toluene diisocyanate or methylene diphenyl particular linear polyurethanes (TPU), polyureas,

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, such as prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines such as hexamethylene diamine 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

Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly-(ether)ketonen, Polysulfonen, Polyethersulfonen, Polyarylsulfonen, Polyphenylensulfiden, Polybenzimidazolen, Polyhydantoinen,

Polyesters of aliphatic or aromatic dicarboxylic acids and diols or hydroxy carboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthylate (PEN), poly-l, 4-dimethylolcyclo-hexanterephthalat, polyhydroxybenzoate, Polyhydroxynaphthalat,

Polylactic acid (PLA), polyhydroxybutyrate (PHB), polyhydroxy valerate (PHV), polyethylene, Polytetramethylensuccinat, polycaprolactone m) polycarbonates, polyester and blends such as PC / ABS, PC / PBT, PC / PET / PBT, PC / PA

n) Cellulosederivaten wie z.B. Cellulosenitrat, Celluloseacetat, Cellulosepropionat, Cellulosebutyrat,

o) epoxy resins, consisting of di- or polyfunctional Epoxidverbin- compounds in combination with, for example hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates, or catalytically active 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 such as styrene, alkyd resins,

r) silicones, siloxanes, for example on the basis of dimethyl siloxanes, methyl phenyl or diphenylsiloxanes, for example, vinyl group terminated s) more of the aforementioned polymers, and mixtures, combinations, or blends of two or more.

Long as it is at the specified under a) to r) polymers are copolymers, they may be in the form of statistical ( "random"), block or "tapered" structures. Further may be mentioned the polymers in the form of linear, branched, star-shaped or hyperbranched structures.

Long as it is at the specified under a) to r) polymers are stereoregular polymers, this may take the form of isotactic, stereotactic, but also atactic forms or as Stereoblockcopolymere.

can continue the polymers mentioned under a) to r) both amorphous and (semi) have crystalline morphologies.

Possibly. the polyolefins mentioned under a) can also be crosslinked, for example crosslinked polyethylene, which is then referred to as X-PE.

The polymers mentioned a) to r) can not be present only as new but also in the form of recycled thereby, for example as production waste or recyclable material collection ( "post-consumer" recycled).

are recyclates to a conceptual definition of plastic in a further preferred embodiment, recycled plastics or recycled plastics. On a conceptual definition is here to the standard DIN EN 15347: 2007 refers, in which the term plastic recyclate is fixed. This definition is also used as a basis for the purposes of the present invention.

More preferably, the recycled plastic is selected here from the group consisting of recycled polyesters, in particular recycled polyethylene terephthalate (rPET), recycled polybutylene terephthalate (rPBT) recylcierter polylactic acid (RPLA), polyglycolide recycled and / or recycled polycaprolactone; recycled polyolefins, in particular recycled polypropylene (RPP), recycled polyethylene and / or recycled polystyrene (RPS); recycled thereof polyvinyl chloride (RPVC), recycled polyamides, and mixtures and combinations thereof.

relevant international standards exist for many plastic recyclates. PET plastic recycled materials, for example, the DIN EN 15353: 2007 relevant. PS recyclates are in DIN EN 15342: 2008 described in detail. PE recyclates are in DIN EN 15344: treats of 2008. PP recyclates are in

DIN EN 15345: characterized of 2008. PVC recyclates are specified in DIN EN 15346: 2015 refers closer. For purposes of corresponding specific Kunststoffrecyclate the present patent application makes the definitions of these international standards as our own.

Further, possible to use the present compounds for the stabilization of rubbers and elastomers. There may be natural rubber (NR), synthetic rubber materials or.

If it is in the organic materials to oils and fats, they may or may oils, fats or waxes synthetic based esters for example based on mineral oils, vegetable fats and animal fats. Planzliche oils and fats, for example, palm oil, olive oil, canola oil, linseed oil, soybean oil, sunflower oil, castor oil, animal fats, for example fish oil or beef tallow.

may be further compounds of the invention for the stabilization of low molecular weight or oligomeric polyols used as they are used in the polyurethane production, for example. Suitable hydroxy compounds are, for example, butane-l, 4-diol, oligomeric ethylene glycols or tetrahydrofuran oligomers.

The inventive compounds may further be used as stabilizers for lubricants, hydraulic oils, engine oils, turbine oils, gear oils, metal working fluids or lubricating greases. These mineral or synthetic lubricants are mainly based on hydrocarbons.

Possible and advantageous here is that the plastic fikatoren Rheologiemodi-, for example, the plastics molding composition at least one further additive selected from the group consisting of UV absorbers, light stabilizers, hydroxylamine based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact modifiers, plasticizers, lubricants, , extender containing chains processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, anti-fogging agents and marking agents.

Possible further additives are selected from the groups consisting of UV absorbers, light stabilizers, the stabilizers, the hydroxylamines, the benzofuranones of nucleating agents, impact modifiers, soft-wheeler, lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, anti-blocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, marking agents or anti-fogging agents. In a preferred embodiment, the compositions contained th particular acid scavenger, for example 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, the hydroxylamines, the amines, of the lactones, the thio compounds and / or

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

Suitable light stabilizers are, for example, compounds based on 2- (2 ' hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides, and 2- (2-hydroxyphenyl) -l, 3,5-triazines.

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,

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'- 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.

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.

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.

Geeignete Ester von Benzoesäuren sind beispielsweise 4-tert-Butylphenyl-salicylat, Phenylsalicylat, Octylphenylsalicylat, Dibenzoylresorcinol, Bis(4-tert-butylbenzoyl)resorcinol, Benzoylresorcinol, 2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoat, Hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoat, Octa-decyl-3,5-di-tert-butyl-4-hydroxybenzoat, 2-Methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoat.

Suitable oxamides are 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.

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.

Suitable phenolic antioxidants include:

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;

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;

Such as 2,6-di-tert-butyl-4-methyoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol hydroquinones and alkylated hydroquinones , 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 -hydroxyphenylstearat, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate; Tocopherols such as α-, ß, γ-, δ-tocopherol and mixtures thereof (vitamin E);

hydroxylierte Thiodiphenylether, wie z.B. 2,2'-Thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-Thiobis(4-octylphenol), 4,4'-Thiobis(6-tert-butyl-3-methyl- phenol), 4,4'-Thiobis(6-tert-butyl-2-methylphenol), 4,4'-Thiobis(3,6-di-sec-amylphenol), 4,4'-Bis(2,6-dimethyl-4-hydroxyphenyl)disulfid; Alkylidenbisphenole, wie z.B. 2,2'Methylenbis(6-tert-butyl-4-methylphenol), 2,2'-Methylenbis(6-tert-butyl-4-ethylphenol), 2,2'-Methylenbis[4-methyl-6-(a-methylcyclohexyl)phenol], 2,2'-Methylenbis(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;

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;

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;

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;

Benzylphosphonate, wie z.B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonat, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Di-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonat, Dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonat, das Calciumsalz des Mono-ethylesters der 3,5-Di-tert-butyl-4-hydroxybenzylphosphonsäure;

Acylaminophenole, wie z.B. 4-Hydroxylauranilid, 4-Hydroxystearanilid, Octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamat;

Ester der ß-(3,5-Di-tert-butyl-4-hydroxyphenyl)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, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxyethyl)isocyanurat, N,N'-Bis(hydroxyethyl)oxamid,

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

Esters of .beta. (tert-butyl-5-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, for example methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol,

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, 3,9-Bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-l,l-dimethylethyl]- 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;

Ester der 3,5-Di-tert-butyl-4-hydroxyphenyl)essigsäure mit ein- oder mehrwertigen Alkoholen, z.B. Methanol, Ethanol, Octanol, Octadecanol, 1,6-Hexan-diol, 1,9-Nonandiol, Ethylenglycol, 1,2-Propandiol, Neopentylglycol, Thiodiethylenglycol, Diethylenglycol, Triethylenglycol, Pentaerythritol, Tris(hydroxy-ethyl)isocyanurat, N,N'-bis(hydroxyethyl)oxamid, 3-Thiaundecanol, 3-Thia-pentadecanol, Trimethylhexandiol, Trimethylolpropan, 4-Hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octan;

Amides of the SS (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as Ν, Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylendiamid, Ν, Ν ' -bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylendiamid, Ν, Ν'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylendiamid, Ν, Ν'-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).

Particularly preferred phenolic antioxidants are the following structures:



Suitable phosphites / phosphonites include:

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)phosphit], 2-Ethylhexyl(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl))phosphit, 5-Butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-l,3,2-dioxaphosphiran.

Other suitable phosphites are the commercial products Weston 705 (manufactured Addivant) and Doverphos LGP 11 (manufactured by Dover Chemical Corporation), where it is liquid phosphite.

Particularly preferred phosphites / phosphonites are:



, Where n> 1

Suitable amine antioxidants include:

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-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, Ν, Ν, Ν ', Ν'-tetra-methyl-4,4'-diaminodiphenylmethane, l, 2-bis [(2-methyl-phenyl) amino] ethane, l, 2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (l ', 3'-dimethylbutyl) phenyl] amine, ieri-octylated N-phenyl-l-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 / lsohexyl-diphenylamines, a mixture of 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, Ν, Ν, Ν ', Ν'-tetraphenyl-l, 4-diaminobut-2-ene, and mixtures or combinations thereof.

Other suitable aminic antioxidants are hydroxylamines or N-oxide (nitrones), such as Ν, Ν-dialkylhydroxylamines, N, N-Dibenzylhydroxyl-amine, N, N-dilaurylhydroxylamine, Ν, Ν-distearylhydroxylamine, N-benzyl-a-phenylnitrone , N-octadecyl-a-hexadecyl, and Genox EP (Addivant) according to the formula:

R, , Rs - C14- C24 Alkyl

Genox EP

Other suitable stabilizers are thiosynergists. Thio-synergists suitable are, for example, distearyl thiodipropionate, dilauryl thiodipropionate, or the compound according to the following formula:

Other suitable stabilizers in particular of polyamides are copper salts such as copper (I) iodide, copper (I) bromide or copper complexes such as triphenyl phosphine-copper (I) complexes

Suitable hindered amines are for example l, l-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (l, 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (l octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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-di-ch loro-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-tetramethylpiper- azinon), 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- tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro- [4,5] decane and epichlorohydrin.

Preferred hindered amines continue to have the following structures:

33

Preferred oligomeric and polymeric hindered amines have the following structures:

Geeignete Lactone sind bespielsweise: 5,7-di-tert-butyl-3-(3,4-dimethyl-phenyl)-3H-benzofuran-2-on, 5,7-di-tert-butyl-3-[-4-(2-stearoyloxyethoxy)-phenyl]-benzofuran-2-on, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-οη), sowie phosphorhaltige 3-Phenylbenzofuran-2one.

Suitable metal deactivators include for example Ν, Ν'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4- hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-l, 2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl, Sebacoylbis-phenylhydrazide, Ν, Ν'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxylyldi hydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

Suitable dispersants are for example:

Polyacrylates, such as copolymers with long-chain side groups, polyacrylate block copolymers, alkyl amides: for example N, N'-l, 2-Ethandiylbisoctadecanamid sorbitan esters, for example Monostearylsorbitanester, titanates, and zirconates, reactive co-

polymers having functional groups, for example, polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, Pol-ystyrol-alt-maleic anhydride polysiloxanes: for example, dimethyl silane diol-ethylene oxide copolymer, polyphenylsiloxane copolymer Amphiphilic Copolymer-re: eg polyethylene-block-polyethylene oxide, dendrimers, including hydroxylgrup-penhaltige dendrimers.

Suitable nucleating agents are, for example, talc, alkali or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as benzoic acid, succinic acid, adipic acid, for example sodium benzoate, Zinkglycerolat, aluminum-hydroxy-bis (4-te / t-butyl) benzoate, benzylidene sorbitols such as 1,3 : 2,4-bis (benzylidene) sorbitol or l, 3: 2,4-bis (4-methylbenzylidene) sorbitol, 2,2 ' -methylene-bis- (4,6-di-te / t-butylphenyl) phosphate and trisamides and diamides such as Trimesinsäuretricyclohexylami, Trimesinsäuretri (4-methylcyclohexylamide), trimesic acid tri (tert.butylamid), N, N ' , N " -1,3,5 Benzoltriyltris (2,2-dimethyl-propanamide) or 2 , 6-Naphthalindicarbosäuredicyclohexylamid.

Suitable Antinukleierungsmittel for example, azine dyes such as nigrosine, ionic liquids and / or lithium salts.

Suitable flame retardants are for example:

a Inorganic flame retardant) such as AI (OH) 3 , Mg (OH) 2 ,

AIO (OH), MgC0 3 , not or organically modified sheet silicates such as montmorillonite or sepiolite, double salts such as

Mg-Al-silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite and Sb 2 0 3 , Sb 2 0 5 , Mo0 3 , zinc stannate, zinc hydroxystannate,

b) Nitrogen-containing flame retardants such as melamine, melem, melam, melon, melamine derivatives, Melaminkondensationsproduk- te or melamine salts, benzoguanamine, polyisocyanurates, allantoin, Phosphacene, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine-metal phosphates such as metal laminaluminiumphosphat, melamine zinc phosphate, melamine

magnesium phosphate, and the corresponding pyrophosphates and polyphosphates, poly [2,4- (piperazin-l, 4-yl) -6- (morpholin-4-yl) -l, 3,5-triazine], ammonium polyphosphate, melamine borate, Mela - minhydrobromid,

c) free radical generator, such as alkoxyamines, hydroxylamine,

Azo compounds, sulfenamides, sulfenimides, dicumyl or Polycumyl, hydroxyimides and their derivatives, such as

Hydroxyimidester oder Hydroxyimidether

d) Phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate, and their oligomers, triphenyl phosphate, Ethylendiamindiphos- phosphate, phosphinates such as salts of hypophosphorous acid and its derivatives such as Alkylphosphinatsalzen example Diethylphosphinat- aluminum or diethyl phosphinate-zinc or Aluminiumphos- phinat, aluminum phosphite, Aluminiumphosphonat, phosphonate ester, oligomeric and polymeric derivatives of Methanphosphon- acid, 9,10-dihydro-9-oxa-10-phosphorylphenanthren-10-oxide (DOPO) and their substituted compounds,

e) Halogen-containing flame retardants and bromine-chlorine such as polybrominated diphenyl oxides, such as Decabromdi- phenyl oxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, 1,2- bis (tribromophenoxy) ethane, hexabromocyclododecane, brominated diphenylethane, tris (2,3-dibromopropyl) isocyanurate, ethylene-bis- (tetrabromophthalimid), tetrabromo-bisphenol A, brominated

Polystyrene, brominated polybutadiene or polystyrene-polybutadiene brominated copolymers, brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl, optionally in combination with Sb 2 0 3 and / or Sb 2 0 5 ,

f) borates such as zinc borate or Caiciumborat, optionally on support material such as silica

g) Sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamate, mercaptobenzothiazole and sulfenamides,

h) Antidrip agents such as polytetrafluoroethylene,

i) silicon-containing compounds such as Polyphenylsiloxane, j) carbon modifications such as carbon nanotubes (CNT), expandable graphite or graphene

k) as well as combinations or mixtures thereof.

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

Suitable pigments may be inorganic or organic. Inorganic pigments are for example titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example,

Anthrachinone, Anthanthrone, Benzimidazolone, Chinacridone,

Diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Other suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.

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

Suitable optical brighteners are, for example, bisbenzoxazoles,

Phenylcoumarins or bis (styryl) biphenyls and in particular optical brightener of the formulas:

Suitable filler deactivators are for example polysiloxanes,

Polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth) acrylates and their copolymers, for example, with styrene as well as epoxides, for example, the following structures:

n = 1-10

Suitable antistatic agents include, for example, ethoxylated alkyl amines, fatty acid ester, alkyl sulfonates, and polymers such as polyether amides.

Suitable Antiozonantien are the aforementioned amines such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, Ν, Ν'-bis (l, 4-dimethylpentyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (l, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (l-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.

Suitable mold release agents are, for example montan waxes.

The incorporation of the stabilizers and / or additive composition and optionally the additional additives in the plastic material is made by conventional processing methods, the polymer is melted and mixed with the OF INVENTION-to the invention the additive composition and optionally further additives, preferably by mixers, kneaders and extruders , are as preferred processing machines such as extruders single screw extruder, twin-screw extruders, planetary-gear extruder, ring extruder, co-kneader, which are preferably equipped with a vacuum degassing. The processing may in this case under the absence of air or possibly under inert gas such as

carried a blanket of nitrogen.

may continue to the additive compositions in the form of masterbatches or concentrates, for example, 20-90% of the additives to the invention OF INVENTION-or additive compositions in an

Polymers include, are prepared and introduced. Concentrates are further preferably comprised of the additive and / or the additive composition, and a lubricant. 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. this con-

concentrates can then be in the form of compacted, granulated or extru-all official product forms.

Next, it is advantageous if, in addition selected for the stabilization of organic materials to the compound of general formula I at least one further primary and / or secondary antioxidant, in particular at least one further primary and / or secondary antioxidant is selected from the group consisting of phenolic antioxidants, phosphites, phosphonites , amines, hydroxylamines, and mixtures or combinatio-nen is used thereof.

In the event that it is, the organic materials to plastic compositions or polymer compositions, which contain stabilizers of the present invention, they are suitable in particular for further processing to special shaped parts such as injection-molded parts, foils or films, foams, fibers, cables and pipes, profiles, hollow bodies,

Tapes, membranes, such as geomembranes, which are produced by extrusion, injection molding, blow molding, calendaring, pressing method, spinning processes, rotational molding or String and coating processes, eg for the electrical and electronics industry, construction industry, transport industry (car, plane, ship, Bahn), for medical applications, for household and electrical appliances, vehicle parts, consumer products, packaging, furniture, textiles. These parts belong equally to the present invention.

Preferably compositions of the invention consist of 0.01-5.0% of the stabilizers according to the invention 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 % by weight of the invention stabilizers, 0-3.0% of a further additive and from 97 to 99.98% of a polymer, are very particularly preferably 0.05 to 2% by weight of the stabilizers according to the invention, 0-2% by weight of a further additive and 98 -99.95% by weight of a polymer.

The present invention also relates to an organic material to

Purposes of stabilizing at least one stabilizer or a mixture of several stabilizers according to general formula I, as defined above, includes. For the purposes of the corresponding stabilized organic material to all the above statements apply to the general formula I in the same manner. In particularly preferred manner, the organic material is a plastic composition, in particular with the polymers as previously described standing.

In addition, the invention relates to a process for the stabilization of organic

Materials, in particular plastic compositions, particularly preferably against oxidative, thermal and / or actinic degradation, in which a compound or more compounds according to general formula is incorporated into the organic material I. The incorporation can take place in any known by the prior art.

The present invention also relates particularly efficient stabilizers which are characterized in more detail in the following formulas:

Formel II

wherein R 2 to R 5 , R 7 to R 10 are as defined above, Y and A, with the proviso that in the fragment AX a sulfur atom and n = 1

formula 111

wherein X, n and B is as defined above; such as

Formel IV

wherein A is as defined above.

The present invention is further illustrated by the following examples without limiting the invention to the specific details.

Synthesis of the novel stabilizers:

The used for the syntheses absolute toluene (99.8%), lithium diisopropylamide (LDA) and the elemental sulfur (pa,> 99.5%) were purchased from Sigma Aldrich, phenothiazine (98 +%) from Alfa Aesar, acetonitrile, anhydrous diethyl ether and the 1, 6-molar (15%) of n-butyllithium solution in n-hexane of Merck KGaA acquired chlorodiphenylphosphine made by BASF and available. The compound 4,4'-bis (a, a-dimethylbenzyl) diphenylamine (BDBDA) was purchased from TCI Tokyo Kasei, as well as of absolute tetrahydrofuran from Acros Organics. 2-chloro-5,5-dimethyl-l, 3,2-dioxa-phosphorinane (DDP-CI) was obtained in a manner known from the literature from phosphorus trichloride and l, 3-dimethylpropane-l, 3-diol synthesized.

Embodiment 1

Synthesis of phenothiazine DOP:

DOP-CI Phenothiazin Phenothiazin-DOP

In a carefully dried and nitrogen-filled 500 ml three-necked flask equipped with magnetic stirrer, nitrogen inlet and dropping funnel with pressure equalizer, absolute toluene (150 ml) and 47.3 g of a 2 molar lithium diisopropylamide solution in THF (LDA; 0.095 mol) by means of a syringe was added through a septum. Then phenothiazine (17.93 g, 0.090 mol) added in a nitrogen countercurrent. In the slightly heated dropping funnel absolute toluene (120 mL) (g 21:23, 0.090 mol) via syringe through a septum and molten DOP-CI added in a nitrogen countercurrent (the bottle with the DOP-CI was previously heated to about 100 ° C to melt the reagent). The DOP-Cl solution was added over 30 min with stirring at room temperature dropwise. Subsequently, the reaction mixture was stirred for 1 h at room temperature. After the solids had (mainly lithium chloride) is deposited at the bottom of the piston or the piston wall, the supernatant solution under inert conditions was decanted. To the residue 80 ml of absolute toluene was added by a syringe through a septum. It was stirred for 30 min at 45 ° C and decanted after the solids have settled. Both solutions were combined and the toluene was removed under vacuum. The residue obtained was dissolved in 80 ml of dry acetonitrile under heating. On cooling, the phenothiazine DOP was eliminated. After storing the well sealed piston in a refrigerator (ca. 15 h), the supernatant was separated by decantation. Finally, the adhering solvent was removed in vacuo.31P-NMR (300 MHz, CDCI3, 8) δ = 94.2 ppm. 1H-NMR (300 MHz, CDCI3, 8) δ = 7.86 - 6.77 (m, 16.3H) ppm.

Embodiment 2

Synthesis of phenothiazine DOPS:

Phenothiazin-DOP Phenothiazin-DOPS

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

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

Embodiment 3

Synthesis of phenothiazine PPh2:

Ph,PCI PTZ PTZ PPh,

In a thoroughly dried and filled with nitrogen, 250 ml three-necked flask equipped with magnetic stirrer, dropping funnel and nitrogen inlet, absolute toluene (40 mL) and LDA (7 ml, 0.014 mol) g by a syringe through a septum and phenothiazine (2.39 0.012 mol) was added in a nitrogen countercurrent heated for dissolving at about 40 ° C and then cooled in an ice bath. Then absolute toluene and chlorodiphenylphosphine were (2.65 g, 0.012 mol) was added by a syringe through a septum in a nitrogen countercurrent to a dropping funnel and added dropwise within 10 minutes. The reaction mixture was stirred for 1 h in an ice bath. The NMR spectroscopy of the reaction solution showed that the desired product had formed.

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

Embodiment 4

Synthesis of phenothiazine PPh2S:

PTZ_PPh2 PTZ_PPh2S

In a thoroughly dried and filled with nitrogen, 250 ml three-necked flask equipped with magnetic stirrer, reflux condenser and nitrogen inlet, absolute toluene (60 ml) (g 0.42, 0.013 mol) via syringe through a septum and elemental sulfur in a nitrogen countercurrent to in embodiment 3 where the reaction solution obtained. 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 removing the toluene by distillation in vacuo, re-cooled and the precipitate filtered off again. The product of acetonitrile was recrystallized. The yield was 2.74 g (54%). The NMR spectroscopic investigation showed

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

Embodiment 5

Synthesis of phenothiazine DDP:

DDP-CI phenothiazine phenothiazine-DDP

In a thoroughly dried and filled with argon, 100 ml three-necked flask equipped with magnetic stirrer, septum and argon inlet were absolute THF (40 ml) and phenothiazine (2.99 g, 0.015 mol). Then were added 9.4 ml of a 15% solution of n-butyllithium in n-hexane (0.015 mol) via a syringe through the septum with stirring. After the flask contents were stirred for 20 min, 2-chloro-5,5-dimethyl-l, 3,2-dioxaphosphorinane (DDP-CI, 2:52 g, 0.015 mol) was added dropwise via a syringe through the septum within 10 minutes.

The reaction mixture was stirred for 2 h at room temperature. The NMR spectroscopic analysis of the reaction solution showed that phenothiazine DDP was born.

31P-NMR (300 MHz, CDCI3) δ = 127.0 ppm.

Embodiment 6

Synthesis of phenothiazine DDPS:

To that obtained in Embodiment 5 solution of phenothiazine-DDP in THF was elemental sulfur (0.48g, 0.015 mol) was added in an argon countercurrent. Then was stirred for 3 h at 50 ° C. Thereafter, the solvent was in

Removed in vacuo, and the residue was recrystallized from acetonitrile. The yield of spectroscopically pure phenothiazine DDPS was 85%.

31P-NMR (300 MHz, CDCI3) δ = 56.1 ppm. XH-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,

CH3) ppm. 13C-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

Melting point (° C): 205

Embodiment 7

Synthesis of BDBDA-DOP:

The apparatus used was thoroughly dried. The synthesis was carried out under nitrogen atmosphere.

In a 250-ml three-necked flask equipped with magnetic stirrer, dropping funnel and argon inlet, was added 4.5 g (0.011 mol) of 4,4'-bis (a, a-dimethylbenzyl) diphenylamine (BDBDA) was added. Then, about 30 minutes was at about 0.02 mbar in an oil bath (85 ° C). After cooling to room temperature and filling the flask with nitrogen, 50 ml of dry toluene was added via syringe. Subsequently, 6.9 ml of a 15% solution of n-butyllithium in n-hexane (0.011 mol) was added via syringe over 10 min. The reaction mixture was heated to about 40 ° C and then cooled with an ice bath. Then a solution of 2.6 g (0.011 mol) in abs DOP-CI was. Toluene (30 ml) was added dropwise within 10 min. Thereafter, the reaction mixture was stirred for 1 h at room temperature. Next, the lithium chloride was filtered under inert conditions. The resulting solution of BDBDA-DOP was used for embodiment. 9

31P-NMR (300 MHz, CDCI3) δ = 79,9 ppm.

Embodiment 8

Synthesis of BDBDA DOPS:

To that obtained in Embodiment 7 solution of BDBDA-DOP in toluene was elemental sulfur (0.45 g, 0.014 mol) was added. Then was stirred for 3 h at 80 ° C. Thereafter, the solvent was removed in vacuo. The residue thus obtained was recrystallized twice from acetonitrile.

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

31P-NMR (300 MHz, CDCI3) δ = 66,0 ppm.

Embodiment 9

Synthesis of BDBDA-DPHP:

The apparatus used was thoroughly dried. The synthesis was carried out under nitrogen atmosphere.

In a 250-ml three-necked flask equipped with magnetic stirrer, dropping funnel and argon inlet, was 6.1 g (0.015 mol) of 4,4'-bis (a, a-dimethylbenzyl) diphenylamine (BDBDA) was added. Then, about 30 minutes was at about 0.02 mbar in an oil bath (85 ° C). After cooling to room temperature and filling the flask with nitrogen, 50 ml of dry toluene was added via syringe. Subsequently, 9.4 ml of a 15% solution of n-butyllithium in n-hexane (0.015 mol) was added via syringe over 10 min. The reaction mixture was stirred for 30 min. Then, a solution of 3.3 g (0.015 mol) in abs DPHP-CI was. Toluene was added dropwise within 10 min (30 ml). Thereafter, the reaction mixture was stirred for 3 h at room temperature. Next, the lithium chloride was filtered under inert conditions.

31P-NMR (300 MHz, CDCI3) δ = 54,9 ppm.

Embodiment 10

Synthesis of BDBDA-DPhPS:

To that obtained in Embodiment 9 solution of BDBDA-DPHP in toluene was elemental sulfur (0.58g, 0.018 mol) was added. Then was stirred for 3 h at 60 ° C. Thereafter, the solvent was removed in vacuo. The residue thus obtained was recrystallized twice from acetonitrile. The off yield of spectroscopically pure BDBDA-DPhPS was 78% (based on

DPhP-CI).

31P-NMR (300 MHz, CDCI3) δ = 62,3 ppm.

In a thoroughly dried and filled with argon, two-liter three-necked flask equipped with magnetic stirrer, dropping funnel and argon inlet, were 206.8 g of 4,4'-bis (a, a-dimethylbenzyl) diphenylamine (BDBDA) was added. Then, about 30 minutes was at about 0.02 mbar in an oil bath (85 ° C). After cooling to room temperature and filling the flask with nitrogen, 500 ml of dry THF was added via syringe. a colorless solution was formed. To this was added in the course of about 60 min about 323 ml of a 1.6 molar solution of n-butyllithium in n-hexane was added dropwise with stirring (via syringe). Here, the flask was cooled with a water bath. a yellow solution, which was stirred for 30 minutes it was.

Then, using a syringe approximately 84.3 g DDP-CI in the course of about 90 min with stirring was added dropwise (piston still in the water bath). In the course of reagent addition, the yellowing was paler and after approximately two-thirds of the DDP-CI had been added, the reaction mixture became cloudy. Then, 100 ml of dry n-hexane was added with stirring to cause the precipitation of still dissolved LiCl. It was stirred for a few minutes. The flask with the product solution was stored overnight at room temperature under nitrogen. The precipitated LiCl was removed by decanting under inert conditions. Then, most of the volatiles were distilled the solution in a cold trap, in which the pressure was slowly lowered mbar to about 50 and the temperature of the oil bath was raised to 60 ° C. There was obtained a viscous, oily residue which was further heated to about 70 ° C. To this 800 ml of acetonitrile were added through a funnel.

Then the contents of the flask under a nitrogen atmosphere until heated just below the boiling point. It remained a haze, which settled after stopping the stirrer. After cooling the contents of the flask was

Inert conditions decanted into a nitrogen-filled 2L flask. The remaining residue was treated with about 100 ml of acetonitrile, it was heated and filtered through a paper filter (in the 2 liter flask containing the decanted solution). From the combined product solution crystalline product separated on cooling to the piston wall. After about 2 hours, as already considerable quantities of the product were crystallized, the flask was transferred to the refrigerator and stored there overnight. Then, the supernatant solution was separated by decantation. The crude product thus obtained was recrystallized from 750 ml of acetonitrile under a nitrogen atmosphere

recrystallized. The product was extracted by means of filter paper porcelain funnel / (air presence) and then dried in lüterkolben by vacuum a diaphragm pump, said gently heated with a hair dryer and was frequently swirled. It became a white powder (201 g). From the residual solution of the recrystallization a further 10 g of product were isolated. The NMR spectroscopic analysis of the product showed a purity of> 99.5%.

31P-NMR (300 MHz, CDCI3) δ = 121,0 ppm; 1H-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. 13C-NMR (300 MHz, CDCI3, Chrom-Acetylacetonat) 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),

32,3 (d, IC), 30,8 (s, 4C), 22,4 (d, 2C) ppm.

Melting point (° C): 98-99 ° C

Embodiment 12

Synthesis of BDBDA DDPS:

The apparatus used was thoroughly dried.

BDBDA (239.7 g) was introduced, then the apparatus was evacuated x 3 and back filled with nitrogen to remove any adhering moisture. Subsequently, 440 ml of dry THF was added via syringe. A colorless solution was formed. Were added dropwise to the the course of about 70 min 375 ml of a 1.6 molar solution of butyllithium in n-hexane with stirring (via syringe). Here, the flask was cooled with a water bath. A yellow solution, which was stirred for 30 minutes it was. Then, via syringe 97.8 g DDP-CI in the course of about 80 min with stirring was added dropwise (piston still in the water bath) to give a pale yellow suspension was obtained. There was a 31 added P-NMR spectrum of this suspension (CDCI 3) That a full implementation of the DDP-CI showed.

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

The precipitated LiCl was separated by decanting under inert conditions. The solution in a 2L flask was transferred. The salt residue 20 ml THF and 50 ml of cyclohexane was added (to more product contained mostly extract). Then was stirred and the suspension filtered through a filter paper (in the 2L flask with BDBDA-DDP solution). The combined solution was light brown and the sulfurization reaction was then subjected.

The 2 liter flask was fitted with an internal thermometer. Then about 20 g of sulfur in the course of about 15 min was added in four portions with stirring, the flask was immersed in an oil bath. Was to determine an interpreting Licher temperature rise to about 45 ° C. When the temperature had exceeded its maximum, the oil bath was begun with the heating which has been heated in the course of 30 min at 57 ° C. Stirring was continued for 30 min at 50-52 ° C (internal temperature), and then an NMR sample was taken. The 31 P-NMR spectrum of the product solution showed that the

Sulfurization was carried out with very high selectivity.

The solution thus obtained was transferred to a 2 liter one-neck flask. It was ml with 40 warm THF rinsed, as even a small amount of product had crystallized at the bottom of the three-necked flask. In the flask to another product separated from the ground. A sufficiently complete

to achieve crystallization of the product, was on a rotary evaporator approximately half of the solvent THF and n-hexane is distilled (water bath: 40 ° C). The pressure was lowered in small steps. During the distillation, a significant part crystallized out of the product. The verschlosse plans flask was stored overnight in the refrigerator (about 5 ° C).

The crystallized product was siphoned off. Obtained as a beige-colored crystalline solid, its 31 P-NMR and the proton spectrum already exhibit good purity (ca. 99% mol purity in the phosphorus spectrum; also the proton spectrum shows little impurities). Were obtained about 230 g of the substance. The residual solution was washed with water to remove residual LiCl to (the aqueous phase was brown and was discarded). She was heavily concentrated in a rotary evaporator under partial vacuum, with a further product fraction was obtained. Further purification was achieved by recrystallization from acetonitrile and drying in vacuo with gentle heating. A total of 256 grams of pure BDBDA DDPS were as white solid (77% of the theoretical amount).

31P-NMR (300 MHz, CDCI3) δ = 64,1 ppm; XH-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.

Melting point (° C): 133-135

Embodiment 13

Synthesis of BDBDA-DDP from PCI 3 , BDBDA and l, 3-dimethylpropane-l, 3-diol:

The apparatus used was thoroughly dried. The synthesis was carried out under nitrogen atmosphere.

BDBDA (11.4 g) was introduced, then the apparatus was evacuated three times and filled again with nitrogen to eventually on BDBDA powder adhering to remove moisture. Then, 100 ml of absolute

Diethyl ether was added via syringe. The solution thus obtained was cooled to about 10 ° C. Then, 2.8 g of triethylamine and 3.84 g of

Phosphorus trichloride added sequentially with stirring, whereupon a colorless solid precipitated (triethylammonium chloride). It was stirred for three hours at room temperature. Then the triethylammonium chloride was filtered under inert conditions. The solution was concentrated under a partial vacuum. There was a 31 added P-NMR spectrum which only the phosphorus signal from BDBDA-PCI 2 included (300 MHz, CDCI 3 ; δ =

148,8 ppm).

Then, 6 g of triethylamine and 6 gl, 3-dimethylpropane-l, was added 3-diol. After the reaction mixture had been stirred for two hours at room temperature, 50 ml of diethyl ether were added. After that, the precipitated triethylammonium chloride was filtered off and the solvent was evaporated. The remaining residue was crystallized from acetonitrile

recrystallized.

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

P-NMR (300 MHz, CDCI3) δ = 121,0 ppm; XH-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.

Embodiment 14

Synthesis of PhP (BDBDA) 2

The apparatus used was thoroughly dried. The synthesis was carried out under nitrogen atmosphere.

BDBDA (116.4 g) was introduced, then the apparatus was evacuated three times and filled again with nitrogen to remove any adhering moisture. Subsequently, 750 ml of dry diethyl ether was added via syringe. A colorless solution was formed. To this were one hour, 171.3 in the course ml of a 1.6 molar solution of butyllithium in n-hexane under stirring and cooling with an ice-water bath via syringe dropwise. A pale yellow solution of the lithium salt of BDBDA arose. Stirring was continued for 45 min, and then via syringe was 24.52 g PhP-CI 2over 20 min dropwise with stirring to the cooled solution further. First, a haze was due to the elimination of LiCl. At the end of reagent addition is very much product was eliminated. Stirring was continued for another hour with moderate agitation. There was a 31 P NMR spectrum recorded this suspension (CDCI 3 ) that a full implementation of the PhP-CI 2 and very selective product formation showed.

Then, the main part of the volatiles was under a weak vacuum in a cooled using liquid nitrogen, distilled (the flask dipped in a water bath at about 20 ° C). At the end of the distillation could not be stirred more. Finally, stronger vacuum was briefly applied. To the resulting residue 500 ml of absolute toluene were hinzu-

optionally (tip). Then C. with gentle stirring to about 65 ° being heated, and the product was dissolved and only the LiCl not solved remained, which was filtered off under inert conditions. Now, the toluene was under partial vacuum in a cooled using liquid nitrogen, distilled (the flask dipped in an oil bath at about 55 ° C initially, the end of the distillation, the oil bath temperature was up to about 75 ° C increased). As had been the toluene almost completely distilled, the residue solidified. The solid thus obtained was stirred for one hour with 1 liter of acetonitrile under reflux and nitrogen atmosphere. The product was purified Porzellantrich-ter / filter paper sucked (in the presence of air). It was a white crystalline

Filter cake obtained, which was dried under vacuum with moderate heating. The yield of PhP (BDBDA) 2 was 112 g (about 89% of the theoretical amount mö union).

= 86,0 ppm; 1H-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.

Melting point (° C): 116-118

Studies on the stabilizer action in polypropylene:

Attempts to stabilizer effect with polypropylene were carried out at 230 ° C in a twin-screw micro-extruder. It was used polypropylene of the type MOPLEN HP556E and MOPLEN HP500N (products of Lyondell Basell Industries), the previously crushed by a centrifugal mill at 10,000 rpm / min and about 5 at 100 ° C in a vacuum oven were dried h (mbar 20). three extrusion tests were each performed for each polymer additive mixture. The total amount of used in each trial polymer additive mixture was 4 g. In each run, the forces were recorded by means of software in seconds intervals.

In the Tables 1 and 2, the additives used, their concentrations, and the forces acting at different extrusion times forces are recorded (each as average values ​​of three individual experiments). For comparison, extrusions with the established stabilizer system ADK STAB were

A611 / Caesit AV performed as well as pure MOPLEN HP556E or MOPLEN HP5 tested.

Table 1 (experiments with MOPLEN HP 556E)

Table 2 (tests with MOPLEN HP 500N)

Additive force force force force force force

30 s 60 s 120 s 180 s 300 s 600s

(N) (N) (N) (N) (N) (N)

- 550 530 510 480 460 450

Clock 600 0.2% 640 580 560 540 520

ADK-STAB A611

0,2% 610 570 560 540 520 530

PhP(BDBDA)2

0,2% 730 730 750 740 740 730

Ceasit OF 0.2%

BDBDA-DDP

0,2% 600 600 610 600 590 580

Multiple extrusions

For the extrusion of polypropylene type Moplen HP556E LOI was 033L30 the company LyondellBasell used. The experiments were carried out mm on a twin-screw extruder Thermo Scientific Process 11, with a screw diameter of. 11

In a twin-screw extruder a total of 350 g of pure polypropylene, polypropylene, and polypropylene was extruded with an addition of 0.3% Phenothiazin_DOPS (PTZ_DOPS) three times each. After each extrusion, the sample for about 1 h was in a vacuum drying cabinet at 60 ° C dried. Subsequently, 50 g were kept back and extrudes the remaining granules again. The temperature profile used is Table 3, the parameters obtained at each extrusion are shown in Table 4 to Table 6 below.

Table 3: Utilized temperature profile in the extrusions on twin screw extruder.

Table 4: Parameters of three extrusions of pure polypropylene.

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

Queens PP Extrusion 1. 2. 3. Extrusion Extrusion

Speed ​​/ rpm 150 150 150

Throughput / g / h 468 576 552

Melting point / ° C 213-215 214-217 214-217

Melt Pressure / bar 27-29 32-33 30-32

Torque /% 28-30 37-40 33-37

Torque / Nm 3.4-3.6 4.4-4.8 3.9-4.4

Torque / kW 12:05 12:06 to 00:07 12:06 to 00:07

Melt flow measurements were then obtained from all samples that had previously been dried over night in a vacuum oven at about 60 ° C is performed. For this purpose, in each case 3.5 g of the sample at 230 ° C and a weight of 2.16 kg (DIN EN ISO 19069) measured. The measurement of each sample was performed in this case two to three times and the results were then averaged. The MVR of the pure polymer is intended here by the manufacturer at 10.1 cm 3 are / 10min. Table 5 shows the results of these measurements.

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

Polypropylene and polypropylene with an addition of 0.3% phenothiazine DOPS.

Comparing the results of Table 5 shows the very good Stabilsierungswirkung the stabilizers of the invention, as opposed to pure PP no or only a small reduction in molecular weight (= higher MVR) takes place.

Stabilizer effect of the substances according to the invention:

The phosphorus-containing phenothiazine derivatives of the invention were tested in terms of their effect as processing stabilizers. It was investigated how the new additives influence the melt viscosity of polypropylene during the extrusion process (230 ° C). In the tests, the force was measured in the extruder in function of time. The measured force is proportional to the acting torque, and the latter is directly dependent on the melt viscosity. A decrease in the measured force thus indicates polymer degradation on during the extrusion process. For comparison, A611 (0.2%) / AV Caesit the established stabilizer system AD K-bar was (0.1%) tested. Comparative tests with pure polypropylene were also conducted.

As expected, a continuous power take-off during the extrusion process was observed with pure polypropylene. After 10 min, the measured force was only about two-thirds of the measured value s according to the thirtieth When using the established stabilizer blend the force as expected remained constant at first, but she declined after 3 minutes extrusion time significantly, falling to 10 minutes retention time as with pure PP to about two-thirds of the initial value. This means that the comparison system loses its effect after a relatively short extrusion time.

Surprisingly, no change of force during the extrusion was the case of polypropylene, the small amounts of the stabilizers of the invention was added, determined. Even after a long residence time in the extruder (eg., 10 min!) Was no power loss, while the comparison system had long since lost its effect (strong decrease in the measured force).

Thus, the inventive stabilizers showed excellent and compared to comparison shop much more effective.

The experiments showed that with the use of the stabilizers of the invention processing of the polypropylene in the melt (extrusion, injection molding, etc.) is possible without degradation processes.

The primary or secondary antioxidant may in this case be incorporated in the same manner as the compound of general formula I in the organic material.

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

Claims

Use of a compound or mixtures of several Verbindun gene according to general formula I

formula I

in which

the fragment A has the following Matters

wherein each independently

X is a sulfur atom,

n is 0 or 1,

x is 0 or 1,

Z 1 and Z 2 are selected from the group consisting of hydrogen, alkyl aryl radicals, alkylaryl radicals, arylalkyl radicals, heterocyclic radicals, wherein one or more additional fragments A and / or B may be attached to the previously mentioned radicals,

and a group -O-Z 3 , wherein Z 3 is selected from alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals,

and a group -SZ 4 , wherein Z 4 is selected from alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals,

wherein in the case of x = 1, the radicals Z 1 and Z 2 may form together with the phosphorus atom form a ring system to which one or more additional fragments A and / or B may be bonded,

the fragment B has the following meaning

wherein each independently

R 1 to R 10 are selected from the group consisting of hydrogen, alkyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals and heterocyclic radicals, where the radicals R 1 and R 6 may also be connected via a connecting group, the phenyl groups -Y-, wherein Y is selected is selected from the group consisting of S, 0, NH, PH, as well as a covalent bond, wherein the fragments a and B of the phosphorus and the nitrogen atom are joined together by covalent bonding,

and wherein

y is 1 or 2,

wherein x + y = 2,

for the stabilization of 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, metal working fluids, chemicals or monomers.

3. Use according to one of the preceding claims, characterized in that the fragment A is selected from the following radicals

wherein x = y = 1

wherein x = 0 and y = 2, or

wherein x = y = 1

wherein x = y = 1

wherein each independently

R is selected from the group consisting of hydrogen, Al kylresten, aryl radicals, alkylaryl radicals, arylalkyl radicals and heterocyclic radicals,

R 12 is selected from the group consisting of hydrogen, Al kylresten, aryl radicals, alkylaryl radicals, arylalkyl radicals, heterocyclic radicals, where the radicals mentioned above may have also hetero- roatome and / or the above-mentioned radicals A and several other fragments or / or B may be attached, and

X and n are as defined in claim. 1

4. Use according to one of the preceding claims, characterized in that the fragment A is selected from the following radicals

where in each case x = 0 and y = 2, and

wherein x = y = in each case applies. 1

Use according to one of the preceding claims, characterized in that the compound according to general formula I below DEFINE w

wherein X, n and B are as defined in claim. 1

6. Use according to one of the preceding claims, characterized in that the fragment B is selected from the group consisting of the following radicals

wherein y = 1 or 2,

wherein y = 1 or 2, and

wherein y = 1 or 2

in each case independently of one another R 2 to R 5 and R 7 to R 10 and Y are as defined in the claim. 1

7. Use according to one of the preceding claims, characterized in that the fragment B is selected from the group consisting of the following radicals

Use as claimed in any one of the preceding claims, that the compound according to general formula I is selected from the group consisting of the following compounds

70

71

72

wherein each independently

R 11 is selected from the group consisting of hydrogen, Al kylresten, aryl radicals, alkylaryl radicals, arylalkyl radicals, and heterocyclic radicals.

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 sum of all compounds according to general formula I to a weight proportion of from 0.01 to 10 wt .-%, preferably from 0.05 to 5 wt .-%, more preferably from 0.1 to 1.5 wt .-% in the organic material is contained.

Use according to one of the preceding claims, for stabilizing plastics, wherein the plastic is selected from the group consisting of

a) polymers of olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-l,

Polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of random or block structures, such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene vinyl acetate (EVA), ethylene-Acrylester, such as ethylene butyl acrylate, ethylene-acrylic acid and salts thereof

(Ionomers) and 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-polybutyl acrylate-graft-maleic anhydride, and blends thereof,

b) Polystyrol, Polymethylstyrol, Poly-alpha-methylstyrol,

Polyvinylnaphthalene, Polyvinylbiphenyl, polyvinyl toluene, 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, appropriate graft copolymers such as styrene butadiene,

Maleic anhydride onto SBS or SEBS, and graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), as well as 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

Polymethacrylate wie Polymethylmethacrylat (PMMA), Polybutyl- acrylat, Polylaurylacrylat, Polystearylacrylat, Polyglycidylacrylat, Polyglycidylmethacrylat, Polyacrylnitril, Polyacrylamide,

Copolymers such as polyacrylonitrile polyalkyl,

e) polymers from unsaturated alcohols and derivatives, such as

Polyvinylalkohol, Polyvinylacetat, Polyvinylbutyral, Polyallylphthalat, Polyallylmelamin,

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,

Polypropylenglycol, Polyethylenoxid, Polypropylenoxid,

Po lytet ra ra u n I give up,

i) polyurethanes from hydroxyl-terminated polyethers or Polyes- and aromatic or aliphatic isocyanates tern particularly 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 polyphthalamide, for example made of

Terephthalic acid and / or isophthalic acid and aliphatic diamino

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) Polyimiden, Polyamid-imiden, Polyetherimiden, Polyesterimiden, Poly(ether)ketonen, Polysulfonen, Polyethersulfonen,

Polyarylsulfonen, Polyphenylensulfiden, Polybenzimidazolen, Polyhydantoinen,

I) polyesters of aliphatic or aromatic dicarboxylic acids and diols or hydroxy carboxylic acids such as

Polyethylenterephthalat (PET), Polybutylenterephthalat (PBT), Polypropylenterephthalat (PTT), Polyethylennaphthylat (PEN), Poly- 1.4- dimethylolcyclohexanterephthalat, Polyhydroxybenzoat, Polyhydroxynaphthalat, Polymilchsäure (PLA), Polyhydroxybutyrat (PHB), Polyhydroxy-valerat (PHV), Polyethylensuccinat,

Polytetranethylensuccinat, Polycaprolacton,

m) polycarbonates, polyester, and blends such as

PC/ABS, PC/PBT, PC/PET/PBT, PC/PA

n) Cellulosederivaten wie z.B. Cellulosenitrat, Celluloseacetat,

Cellulosepropionat, Cellulosebutyrat,

o) epoxy resins, consisting of di- or polyfunctional Epoxidver- compounds in combination with, for example hardeners based on amines, anhydrides, dicyandiamide, mercaptans, isocyanates, or catalytically active 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,

s) silicone

s) more of the aforementioned polymers, and mixtures, combinations, or blends of two or more.

11. Use according to one of the preceding claims, characterized in that the plastic is at least one further additive selected from the group consisting of UV absorbers, light stabilizers, hydroxylamine based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, Toggle timikrobielle agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, anti-fogging agents, as well as marking agent contains.

12. Use according to any one of the preceding claims, that for the stabilization of organic materials 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.

13. Organic material, in particular plastic composition containing at least one stabilizer or a mixture of several stabilizers according to the general formula I

formula I

wherein A, B and Y are as defined in claim. 1

14. A method for the stabilization of organic materials, especially against oxidative, thermal and / or actinic degradation, in which a compound or more compounds of general formula I

formula I

wherein A, B and Y are as defined in claim 1, in the organic

Material is incorporated.

A compound according to one of the following general formulas II, and IV

Formel II

wherein R 2 to R 5 , R 7 to R 10 are as defined, Y and A in claims 1 and 3, with the proviso that in the fragment AX a sulfur atom and n = 1;

wherein X, n and B is as defined in any one of claims 1, 5 or 7; such as

wherein A is as defined in any one of claims 1, 3 or. 4