Stabilizing compounds. Process for their production.

Composition containing these stabilizing compounds. Process for stabilizing an organic component and use of stabilizing compounds

The present compound relates to novel compounds with a stabilizing effect, in particular stabilization against oxidative thermal and / or actinic degradation or damage to organic materials. The compounds are represented by the general formula I given below. The present invention also relates to a process for the preparation of such compounds, compositions comprising this compound, a process for stabilizing organic components with the aid of the stabilizing compounds and use of the stabilizing compounds for stabilizing organic materials.

Organic materials such as plastics are subject to aging processes, which ultimately lead to a loss of the desired properties such as the lead characteristic values. This process, called autoxidation, leads to changes in the polymer chain, such as in molecular weight or the formation of new chemical groups, starting from radical chain splitting by mechanochemical processes or by UV radiation in the presence of oxygen. Stabilizers are therefore used to prevent or at least delay this aging. Important representatives of stabilizers are antioxidants that interfere with the radicals formed in the autoxidation and thus interrupt the breakdown process. A distinction is generally made between primary antioxidants, which can react directly with oxygen-containing free radicals or C radicals, and secondary antioxidants, which react with intermediately formed hydroperoxides (see C. Kröhnke et al. Antioxidants in Ullmann's encyclopedia of industrial chemistry, Wiley-VCH Verlag, Weinheim 2015). Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines but also lactones. Classes of secondary antioxidants are phosphorus compounds such as phosphites and phosphonites, but also organosulfur compounds such as sulfides and disulfides. The combined use of primary and secondary antioxidants can lead to a synergistic effect. For example, the combinations of phenolic antioxidants with phosphites / phosphonites are known, but also the combinations of phenolic antioxidants with thio compounds (see, for example, I. Vulic et al. Pol. Degr. Stab. 2002, 78, 27-34). Against the background of a synergistic effect, it is therefore also desirable

In principle, sulfur-containing antioxidants, ie stabilizers, which contain both a sterically hindered phenolic group and a thio group in one molecule, are known and are also commercially available in part. Commercial products have, for example, the following structures (trade names, for example: Songnox 4150, Irganox 1081, Irganox 1035, Irganox 1520, Irganox 565, Hostanox OSP 1):

The synthesis and use of these stabilizers is described in numerous patents, examples of which are mentioned: DE 23641126, DD 251128, EP 275832, EP 428973, US 3245992, US 3257354

It is also known that aliphatic thio groups have a lower tendency to discoloration than aromatic thio groups (for example US 2981717), which is generally a desirable property for long-term stability of organic materials.

Further stabilizers which contain both phenolic and thio groups are described in the form of molecules containing isocyanurate in the patent documents US 4727103, US 4633008 and US 4694102. The chemical structures mentioned in these patents are both differentthe structures according to the invention and manufactured by other methods.

When considering the above-mentioned commercial sulfur-containing antioxidants it is striking that there are obviously no commercial products which simultaneously have a high concentration of sterically hindered phenols and a high concentration of aliphatic thio groups.

The object of the present invention was therefore to provide a new process for the production of sulfur-containing antioxidants and new compounds with excellent stabilizing activity for organic materials, in particular for plastics.

This object is achieved with the novel compounds according to general formula I according to claim 1. The production of the corresponding connections is named in claim 7. The present invention also relates to a composition comprising an organic component to be stabilized and one of the compounds according to the invention as claimed in claim 11. The invention also relates to a method for stabilizing a stabilizing organic component as well as uses of stabilizing connections according to the invention according to claim 17. The respective dependent patent claims relate to advantageous embodiments.

The invention thus relates to a compound according to general formula I.

where the variables A, B, D, R, b, x, y, z each independently have the following definition:

A is an aromatic, unsaturated or saturated radical,

BO or NH,

D is a linear or branched aliphatic radical with 1 to 12

Carbon atoms,

R is a radical with at least one sterically hindered group and at least one hydroxyl group,

b 0 or 1,

x 0 to 12,

y 1 is 4,

from 1 to 6.

New stabilizers and a new method for producing the stabilizers are proposed which allow easy access to complex stabilizer structures and are highly effective, for example in polymers. In particular, the high proportion of aliphatic sulfur groups with a high number of sterically hindered phenol groups by the process according to the invention leads to a low tendency to discolouration of the new compounds with simultaneous extraordinary long-term stabilization.

Surprisingly, it has been shown that the above compounds have high stabilizing potential, in particular stabilization of organic materials against oxidative thermal and / or actinic degradation.

A preferred embodiment provides that the variable A is selected from the group consisting of z-valent cyanuric acid residues, where z has the meaning given in claim 1, triazine residues, cyclic aliphatic hydrocarbon residues with 5 to 36 carbon atoms, in particular cyclohexyl, aromatic Hydrocarbon residues, especially phenyl, linear or branched aliphatic hydrocarbon residues with 2 to 36 carbon atoms.

It is also advantageous if the variable R represents a grouping with at least one sterically hindered hydroxyphenyl radical, in particular has the following meaning

in which

E is the same or different in each occurrence and is a linear aliphatic, branched aliphatic, cycloaliphatic alkyl radical with 1 to 18 carbon atoms, an aromatic radical with 6 to 36 carbon atoms or hydrogen, in particular a tert-butyl group or one Represents methyl group,

a is 1 or 0, and

c is 0, 1, 2, 3, or 4.

Both radicals E are preferably identical radicals. However, it is likewise possible for the radicals E to be different, for example one radical E can be hydrogen and the other radical E can be a methyl or t-butyl group.

In particular, the variables x, y and z each independently have the following meaning:

x 0 or 1,

y 1 or 2,

z 1, 2, 3 or 4.

The compound of general formula I according to the invention is preferably selected from the group consisting of the following compounds:

where Z has the following meaning:

and the variables B, D, R, b, x, y and z are as defined in claim 1.

The variable D is selected in particular from the group consisting of

- CH 2 - or a 1, 2, 3-propynyl radical.

Particularly preferred embodiments of the present invention provide

that the compound according to the invention is selected from the group of

following connections:

with each occurrence independently of one another, the radical Y has the following meaning:

or

In the above radicals, the tBu radical can also be wholly or partly substituted by a methyl group and / or hydrogen.

In addition, the present invention relates to a process for the preparation of a compound as defined above according to general formula I, in which a compound according to general formula II

with a thiol according to one of the general formulas IIIa or IIIb

is implemented, and in the event that a thiol of the general formula IIIa was used, then a reaction of the reaction product obtained by reaction of the compounds of formulas II and IIIa with a compound of the general formulas IV

in which

X represents a leaving group, and

the meaning of the variables A, B, D, R, b, x, y, z in the compounds of the formulas IIa, IIb and III are as defined in claim 1.

For specific variations of the variables A, B, D, R, b, x, y, z in the formulas Na, IIb and III mentioned above, reference is made to the explanations above in order to avoid repetition. All of the preferred embodiments for the compound I according to the invention also apply to the formula II, IIIa, IIIb and IV.

The aforementioned leaving group is in particular an alcoholate, halide, trifluoromethanesulfonate, tosylate, mesylate, fluorosulfonate or nonaflate.

The compounds according to the invention are accordingly prepared by means of a thiol-ene reaction or coupling.

The reaction of a thiol with reactive CC double bonds takes place.

The thiol-en coupling is a reaction that is used, for example, for the synthesis of loading

Layering, the production of films and for the modification of polymers is used (see BCE Hoyle, CN Bowman, Angew. Chem. Int. Ed. 2010, 49, 1540-1573; AB Lowe, Polym. Chem. 2010, 1, 17 -36). The use of triallyl cyanurate, which is used, inter alia, as a precursor in the stabilizers according to the invention, as a starting product for the thiol ene coupling is described by Z. Altintas et al. Chinese Journal of Polymer Science 2015, 6, 850-856. This serves as a thioether-functionalized chain extender in thermoplastic polyurethanes; an application as a stabilizer or intermediate product for stabilizers is not described therein or can be derived therefrom. The use of diallyl phthalate, which is also used, inter alia, as a precursor in the stabilizers according to the invention,as a starting product for the thiol-en coupling, Herweh et. al. (US4035337) as an inhibiting agent for (aromatic) amine-induced yellowing. A combination of molecules and use with sterically hindered phenols is not described or derived therefrom. The use of styrene, which is also used, inter alia, as a precursor in the stabilizers according to the invention, as a starting product for the thiol-en coupling, is described, inter alia, by Dazzi (US2642373 A) as a fungicide or by Gluesenkamp (US2617778 A) as a plasticizer for vinyl chloride polymers as well as by Limnios et. al. Adv. Synth. Catal. 2017, 359, 323-328 as a photo-initiated alternative to organocatalytic thiol-olefin additions in possible peptides and glucoside modifications.

In connection with stabilizers / stabilization, the thiol ene reaction in H. Li et al. Polymer Composites 2015 and W. Wu J. Macromol. Be. B 2014, 53, 1244-1257 mentioned. With regard to the reaction principles, which are also valid for the purposes of the present invention, reference is made to these publications. In the first case, a silane is synthesized by adding Michael to an acrylate with a phenolic stabilizer function. In the second case, a polyhydroxylated polybutadiene is first reacted, followed by a reaction with a diisocyanate and a sterically hindered phenol. The two reactions described lead to different chemical products than the stabilizers according to the invention.

The reaction of the compound according to general formula II with the thiol according to one of the general formulas IIIa or IIIb is preferably carried out with an excess of the thiol, based on the unsaturated function of the compound according to general formula II.

In addition, the present invention relates to a composition comprising or consisting of at least one organic component to be stabilized, and at least one compound according to the invention of the formula I as described above.

Stabilizers for thermoplastic, elastomeric and duromeric plastics, in particular in the form of injection molded parts, foils or films, coatings or lacquers, foams, fibers, cables and pipes, profiles, hollow bodies, tapes, membranes, such as geomembranes, or adhesives which are manufactured, for example, by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, rotomoulding or coating and coating processes. The compositions according to the invention are used, for example, for the electrical and electronics industry, construction industry, transport industry (car, aircraft, ship, train), for medical applications, for household and electrical appliances, vehicle parts, consumer articles, packaging, furniture, textiles.Another area of ​​application is lacquers, paints and coatings, as well as oils,

An advantageous embodiment of the present composition provides that the component to be stabilized is selected from the group consisting of plastics, oils, lubricants and greases.

Suitable plastics or polymers, which can be included in the composition according to the invention, are in particular here

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-methyl-penten-1, polybutadiene , Polyisoprene, polycyclooctene, polyalkylene

Carbon monoxide copolymers and copolymers in the form of statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters such as ethylene-butyl acrylate, ethylene-acrylic acid and their salts (ionomers) and terpolymers such as ethylene-acrylic acid-glycidyl acrylate, graft polymers such as polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid, polyethylene-g-acrylic acid,

b) polystyrene, polymethylstyrene, polyvinylnaphthalene, styrene-butadiene (SB), styrene-butadiene-styrene (SBS), styrene-ethylene-butylene-styrene (SEBS), styrene-ethylene-propylene-styrene, styrene-soprene, styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), methacrylate-butadiene-styrene (MBS), methacrylate-acrylonitrile-butadiene-styrene (MABS), styrene-ethylene, styrene-maleic anhydride - Polymers including corresponding graft copolymers such as styrene on butadiene, maleic anhydride on SBS or SEBS,

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,

d) polymers of unsaturated esters such as polyacrylates and

Polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate,

Polyacrylonitrile, polyacrylamides, copolymers such as, for example, polyacrylonitrile-polyalkyl acrylate,

e) polymers of unsaturated alcohols and derivatives, such as

Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral,

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, i) polyurethanes, from hydroxy-terminated polyethers or polyesters and aromatic or aliphatic isocyanates, in particular linear polyurethanes, polyureas,

j) polyamides such as polyamide-6, 6.6, 6.10, 4.6, 4.10, 6.12, 12.12, polyamide 11, polyamide 12 and (partially) aromatic polyamides such as polyphthalamides, for example made from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene,

k) polyimides, polyamide-imides, polyetherimides, polyesterimides, poly (ether) ketones, polysulfones, polyether sulfones, polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins,

L) polyesters from aliphatic or aromatic dicarboxylic acids and diols or from hydroxy carboxylic acids such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate,

Polyhydroxynaphthalate, polylactic acid,

m) polycarbonates, polyester carbonates and blends such as PC / ABS, PC / PBT, PC / PET / PBT,

n) cellulose derivatives such as cellulose nitrate, cellulose acetate, cellulose propionate, cellulose butyrate

o) non-thermoplastic or thermosetting plastics p) as well as mixtures, combinations or blends of two or more of the aforementioned polymers.

If the above polymers are copolymers, they can be in the form of statistical (“random”), block or “tapered” structures or as stereoblock copolymers.

If stereoregular polymers are involved, they can be in the form of isotactic, stereotactic, but also atactic forms.

Possibly. the polymers can also be crosslinked. Crosslinking can take place, for example, by adding radical formers or by radiation such as electron beams, beta or gamma rays during processing or in a subsequent step.

The polymers mentioned can be present not only as new goods but also in the form of recyclates, for example as production waste or from recyclable material collections (“post-consumer” recyclates).

Furthermore, the present compounds can be used to stabilize rubber and elastomers. This can be natural rubber (NR) or synthetic rubber materials.

With regard to the amounts of the compound of the formula I contained, it is preferred if the composition is 95.00 to 99.99 parts by weight, preferably 97.00 to 99.95 parts by weight, particularly preferably 98.00 to 99.90 Parts by weight of at least one component to be stabilized, and 0.01 to 5.00 parts by weight, preferably 0.05 to 3.00 parts by weight, particularly preferably 0.10 to 2.00 parts by weight, contains or consists of at least one compound according to the invention according to general formula I

The composition according to the invention, for example based on plastics, can additionally contain at least one additive. In particular, this at least one additive is selected from the group consisting of UV absorbers, light stabilizers, stabilizers, antioxidants, hydroxylamines, benzofuranones, metal deactivators, filler deactivators, antiozonants, nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers , processing agents, thixotropic agents, processing aids, thixotropic agents. Mold release agents, flame retardants, pigments, dyes, optical brighteners, anti-microbial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters,

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) -1,3,5-triazines.

Suitable 2- (2'-hydroxyphenyl) benzotriazoles are, for example, 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-Butyl-2'-hydroxy-phenyl) benzotriazole, 2- (2'-Hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3' , 5'-Di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2- (3'- sec-butyl-5'-tert-butyl-2'-hydroxy-phenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl- 2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxy-carbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3 '-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2' -hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [ 4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2 '-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH- [2- (2-ethyl-hexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) - 5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2 '-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1, 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H- benzotriazole with polyethylene glycol 300; [R-CH- [2- (2-ethyl-hexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) - 5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2 '-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1, 3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H- benzotriazole with polyethylene glycol 300; [R-CH[R-CH[R-CH-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2') -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert- Butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3' -tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R — CH-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2') -hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert- Butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3' -tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R — CH-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3 ' -tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl ) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3 ' -tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl ) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl- 2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of Transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl- 2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of Transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH2 CH 2 - COO-CH 2 CH 2 +2, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3'- (α, α-dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3' - (1,1,3,3-tetramethylbutyl) - 5 '- (α, α-dimethylbenzyl) phenyl] benzotriazole.

Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4 , 4'-dimethyoxy derivatives of the 2-hydroxybenzo-phenones.

Suitable acrylates are, for example, ethyl-α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, Butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, 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, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

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.

Suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl-1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1.3 , 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- ( 2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyl -oxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4, 6-bis (2,4-dimethyl-phenyl) -1,3,5-triazine,2- [2-Hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine, 2- (2-hydroxy-4 -hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4, 6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl - 1.3.5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-1 , 3,5-triazine.2- {2-Hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine.2- {2-Hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-1,3,5-triazine.

Suitable metal deactivators are, 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, isophthaloyl dihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicylic) N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

Suitable phenolic antioxidants are, for example:

Alkylated monophenols such as 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-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-dinonyl-4- methyl-phenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4- Dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof;

Alkylthiomethylphenols, such as, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol,

2,6-didodecylthiomethyl-4-nonylphenol;

Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 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-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;

Tocopherols, such as, for example, α-, β-, γ-, δ-tocopherol and mixtures of these (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-sec-amylphenol), 4,4'-bis ( 2,6-dimethyl-4-hydroxyphenyl) disulfide;

Alkylidene bisphenols 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'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4th , 6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2, 2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis- (2, 6-di-tert-butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate ], Bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4 -

methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis - (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane;

O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , Tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine,, bis (4-tert-butyl-3-hydroxy-2, 6-dimethyl-benzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso-octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;

Hydroxybenzylated malonates, such as, for example, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxy-benzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate;

Aromatic hydroxybenzyl compounds, such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert- butyl-4-hydroxy-benzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) phenol;

Triazine compounds such as, for example, 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3rd , 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3 , 5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di- tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-T ris (3,5-di tert-butyl-4-hydroxphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate;

Benzylphosphonates, such as, for example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-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;

Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;

Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, eg 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,

3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, eg 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, 3-thiaundecanol, 3 -thiapentadecanol, trimethylhexane, trimethylolpropane,

4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane;

Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, eg 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, trimethylol propane, 4- hydroxymethyl propane, 4-hydroxymethyl 2,6,7-trioxabicyclo [2.2.2] octane;

Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, Ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodi-ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy-ethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol , Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as, for example, 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 (3rd, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl ] oxamide (Naugard ® XL-1, distributed by Uniroyal);

Ascorbic acid (vitamin C).

Particularly preferred phenolic antioxidants are:

Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (3,5- di-tert-butyl 4-hydroxyphenyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-trimethyl-2,4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, N, N'-hexane 1,6-diyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide.

Suitable phosphites / phosphonites are for example:

Triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tri (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpenta- erythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, diisodecylpenta- di-tert-bisthritol -butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl -6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri-phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6- Isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite , Up to 2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-di-benz [d, g] -1,3,2 -dioxaphosphocin, 2,2'2 "nitrilo [triethyltris (3,3", 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)) phosphite, 5-butyl-5-ethyl-2- (2,4,6 -tri-tert-butylphenoxy) -1,3,2-dioxaphosphirane.

Particularly preferred phosphites / phosphonites are:

where n can be between 1 and 100.

Other suitable stabilizers are amine antioxidants.

Suitable aminic antioxidants are, for example:

N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N ' -Bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'- Diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl- p-phenylene diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'- Dimethyl-N, N'-di-sec-butyl-p-phenylene-diamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine , N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine,4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxy-phenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 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, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono -4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxy-phenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenylmethane, 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, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono-4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxy-phenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenylmethane, 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, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono-6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenylmethane, 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, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono-6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-di-aminodiphenylmethane, 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, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono-2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono-2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono-and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazines, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene and mixtures or combinations thereof.

Preferred amine antioxidants are: N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine , N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N ' -phenyl-p-phenylene diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine

Further preferred aminic antioxidants are hydroxylamines or N-oxides (nitrones), such as, for example, N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-α-phenylnitrone , N-octadecyl-α-hexadecylnitrone, and Genox EP (additive) according to the formula:

Other suitable stabilizers are thiosynergists.

Suitable thiosynergists are, for example, distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionat, 3- (dodecylthio) -, 1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] - 1,3-propanediyl] propanoic acid ester.

Further suitable stabilizers, in particular for polyamides, are copper salts such as copper (I) iodide, copper (I) bromide or copper complexes such as triphenylphosphine-copper (I) complexes.

Further suitable stabilizers are benzofuranones and indolinones, such as, for example, 3- (4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- (2-hydroxyethoxy) phenyl) benzofuran-2-one ), 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran -2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di -tert-butyl-benzo-furan-2-one, 3- (2,3-di methylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

Suitable hindered amines are, for example, 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebazate, bis (1 octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert- butyl-4-hydroxybenzylmalonate, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2nd , 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, Tris (2,2,6,6-tetramethyl-4-piperidyl ) nitrilotriacetate, tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '- (1,2-ethanediyl) -bis (3,3,5 , 5-tetramethylpiper-azinone), 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-1,3,5-triazine, the reaction product of 7, 7, 9, 9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4,5] decane and epichlorohydrin.

Preferred are oligomeric and polymeric hindered amines of the following

Structures:

In the case of the compounds mentioned above, n is in each case 3 to 100.

Suitable dispersants are, for example:

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

Suitable nucleating agents are, for example, talc, alkali or alkaline earth metal salts of mono- and polyfunctional carboxylic acids, such as, for example, benzoic acid, succinic acid, adipic acid, for example sodium benzoate, zinc glycerolate, aluminum-hydroxy-bis (4-tert-butyl) benzoate, and benzylidene sorbitols, for example 1,3 : 2,4-bis (benzylidene) sorbitol or 1,3: 2,4-bis (4-methylbenzylidene) sorbitol, 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate, and Trisamides and diamides such as trimesic acid tricyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butylamide), N, N ', N "-1,3,5-benzenetriyltris (2,2-dimethyl-propanamide) or 2.6 - Naphthalenedicarboxylic acid dicyclohexylamide.

Suitable antinucleating agents are azine dyes such as nigrosine.

Suitable flame retardants include:

a) Inorganic flame retardants such as Al (OH) 3 , Mg (OH) 2 , AIO (OH), MgCO 3 , layered silicates such as montmorillonite or sepiolite, not or organically modified, double salts such as Mg-Al silicates, POSS- (Polyhedral oligomeric silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxystannate,

b) Nitrogen-containing flame retardants such as melamine, meier, melam, melon, melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allane

toin, 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, and the corresponding pyrophosphates and polyphosphates, poly- [2,4- , 4-yl) -6- (morpholin-4-yl) -1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide,

c) radical formers such as alkoxyamines, hydroxylamine esters, azo compounds, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxyimide ethers d) phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A oligomer, and their Triphenylphosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and their derivatives such as alkylphosphinate salts such as diethylphosphinate aluminum or diethylphosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphonate, phosphonate esters, oligomeric and phosphonic acid, polymeric 9 derivatives 10-dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO) and their substituted compounds,

e) Halogen-containing flame retardants based on chlorine and bromine, such as, for example, polybrominated diphenyl oxides, such as, for example, decabromodiphenyl 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- (tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or, polystyrene-brominated polybutylene-brominated copolyol brominated polyphenylene ether, brominated epoxy resin, polypentabromobenzyl acrylate, possibly in combination with Sb 2 O 3 and / or Sb 2 O 5 ,

f) Borates such as zinc borate or calcium borate, if appropriate on a carrier material such as silica

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

h) antidrip agents such as polytetrafluoroethylene,

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

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 spheres (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers from natural products such as cellulose or synthetic fibers. Other suitable fillers are hydrotalcites or zeolites or layered silicates such as, for example, montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.

Suitable pigments can be inorganic or organic in nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines. Other suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.

Suitable chain extenders for the linear molecular weight build-up of polycondensation polymers such as polyesters or polyamides are, for example, diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyl lactams, bis-maleimides, dicyanates, carbodiimides. Other suitable chain extenders are polymeric compounds such as, for example, 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 brighteners of the formulas:

Suitable filler deactivators are, for example, epoxides such as, for example, bisphenol-A diglycidyl ether, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide.

Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as polyetheramides.

Suitable antiozonants are the amines mentioned above, for example 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, N-cyclohexyl-N'-phenyl-p-phenylenediamine

Suitable mold release agents are, for example, montan waxes.

The following additives, selected from the group consisting of phosphites, phosphonites, hydroxylamines or nitrones, are very particularly preferably present in the composition according to the invention.

In addition, the present invention relates to a method for stabilizing an organic component to be stabilized, in particular against oxidative, thermal or actinic degradation or damage, in which at least one compound is mixed with or incorporated into the organic component to be stabilized.

Preferred embodiments of such a stabilization method provide, for example, that the compound according to the invention is in the form of a powder, Granules, solution, liquid, suspension, emulsion or flakes can be present and with the organic component to be stabilized, in particular the polymer or plastic mixture to be stabilized, the polymer matrix is ​​transferred into the melt and then cooled. Alternatively, it is also possible to introduce the compound of the formula I into a polymer melt in a molten state.

In the event that further constituents are added to the polymer composition, these can be added to the polymers separately, in the form of liquids, powders, dispersions, emulsions, granules or compacted products, or together with the additive composition according to the invention, as previously described be added.

The compounds according to the invention according to formula I and, if appropriate, the additional additives described above are incorporated into the plastic by customary processing methods, the polymer being melted and mixed with the compounds according to formula I according to the invention and any further additives, preferably using mixers, kneaders and extruder. Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place in air or, if appropriate, under inert gas conditions, for example under nitrogen.

Furthermore, the compounds of the formula I according to the invention can be prepared and introduced in the form of so-called masterbatches or concentrates which, for example, contain 10-90% of the compositions according to the invention in a polymer.

In addition, the present invention relates to the use of the compounds of the formula I according to the invention for stabilizing organic materials against oxidative degradation or oxidative damage.

The present invention is explained in more detail with reference to the following explanations, without restricting the invention thereto.

Preferred versions:

Procedure:

In a first reaction step, the reaction of an allyl compound or vinyl compound or Michael acceptor with a thiol compound which additionally has an alcohol group is preferably carried out with the aid of a catalyst and in a second reaction step the transesterification of the alcohol group with an ester compound which is steric contains hindered phenol group. Particularly preferred as the thiol compound are 2-mercaptoethanol, 3-mercaptopropanol, 2-mercaptopropanol and 1-mercaptobutanol and thioglycerol. Another preferred method is the reaction of a thiopropyl compound containing a sterically hindered phenol group, such as

The reaction is preferably carried out in the presence of a catalyst, preferred catalysts are radical-generating compounds such as photo-initiators, azo starters or peroxides and bases for Michael acceptors such as sodium methoxide, triethylamine or nucleophiles such as 1-methylimidazole or alkylphosphines such as dimethylphenylphosphine.

The reaction can be carried out either in bulk or in a solvent; preferred solvents are inert solvents such as toluene, N-methyl-2-pyrrolidone or N, N-dimethylformamide. Methanol is also used as a solvent. Particularly preferred reactions in bulk are preferably carried out in excess of the thiol component as solvent / diluent.

The second reaction step, if necessary, is preferably carried out by transesterification of the intermediate alcohol group with an ester carrying the sterically hindered phenol group. Corresponding processes and catalysts for transesterification reactions are known to the person skilled in the art and are described, for example, in J. Otera, Chem. Rev. 1993, 93, 1449-1470 (see plant) or also in WO 86/00301 (see plant) or W02004 / 033699 ( see attachment). Preferred catalysts are metal compounds such as those from

Group of tin organyles or titanates.

Use:

Preferred organic materials that can be stabilized with the stabilizers according to the invention are plastics, as well as oils and fats.

If the organic materials are oils and fats, they can be based on mineral oils, vegetable fats or animal fats or oils, fats or waxes based on, for example, synthetic esters. Vegetable oils and fats are, for example, palm oil, olive oil, rapeseed oil, linseed oil, soybean oil, sunflower oil, castor oil, animal fats are, for example, fi-oils or beef tallow.

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 mainly based on hydrocarbons.

Embodiments

I. General synthesis regulation

The stabilizers according to the invention are prepared by firstly adding an allyl / vinyl compound in a suitable reaction vessel with a stirrer at room temperature or at elevated temperature with the thiol compound carrying the alcohol group, preferably with the addition of a photocatalyst with UV exposure (method A), a radical starter with heating (method B) or for electron-withdrawing groups (EEC), preferably with the addition of a base (method C) according to the following scheme:

Method A

Method B

Method C

The starting materials are preferably destabilized or degassed before the start of the reaction. The reaction and exposure time of method A is included

30-60 minutes. The reaction time for method B is 4-35h. Appropriately

is a reaction under inert gas conditions for method B. Method C takes a few minutes to react. The purification takes place in water or under high vacuum at 60-100 ° C. In the second step, the esterification with a sterically hindered phenol group is carried out in the

slight excess at temperatures of 130-180 ° C under metal catalysis

according to the scheme:

The resulting alcohol is created by applying a vacuum in the 800-20 range

mbar removed from the reaction mixture. The purification is carried out under high vacuum or aqueous. It is advisable to add bleaching earth or another adsorbent after absorption in solvent to remove metallic catalyst residues by adsorption.

II. Synthesis of Examples According to the Invention

a) Synthesis of Example A According to the Invention:

According to scheme 1

Scheme 1

15.0 g (0.06 mol, 1 eq) of triallyl isocyanurate with 14.2 g (0.182 mol, 3.02

Eq) 2-mercaptoethanol in a round-bottomed flask with a magnetic stirrer underneath

Homogenized stirring at RT. 0.1% by weight of phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator, based on the isocyanurate) is added to the mixture.

added and it is for 30-40 min under UV exposure at λ = 366 nm and

RT stirred. The reaction is controlled by 1 H NMR analysis. The transparent, low-viscosity solution is taken up in 150 ml of ethyl acetate and

twice with 50 ml dist. Washed water, the organic phase is separated off and the solvent is removed under high vacuum at 60.degree. It

27.6 g (95%) of a transparent, highly viscous gel are obtained.

According to scheme 2

Scheme 2

10 g (0.021 mol, 1 eq) of the thioether are mixed with 18.26 g (0.062 mol, 3. 02

Eq) methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate in one

Schlenk flasks with magnetic stirrer, condensation bridge and cold trap with vacuum connection melted under nitrogen at 80 ° C. To the clear

Melt 0.15 mol% n-Bu 2 SnO (based on the thioether) is added, the reaction mixture is heated to 150 ° C. and for ~ 4 h at ~ 50 mbar

touched. The reaction is controlled by 1 H NMR analysis. After done

Implementation, the vacuum is increased to <5 mbar and remaining 3- (3,5-di-tert.

Condensed methyl butyl-4-hydroxyphenyl) propionate. The vacuum

is terminated with N 2 and the reaction mixture is cooled to RT

the melt solidifies into a hard, glass-like mass. The transesterification product is taken up in toluene and concentrated twice with 50 ml.

NaHCO 3 solution and then twice with dist. Washed water until pH neutral. The organic phase is dried over Na 2 SO 4 ,

Filtered through a glass suction filter and the solvent removed under vacuum. A hard, glassy solid solid of 19.6 g (75%) remains.

The structure was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, CDCI 3 ) d = 6.91 (s, 6H, -C arom. -H), 5.00 (s, 3H, -C arom. -OH),

4.15 (t, 6H, -COOCH 2 -), 3.92 (t, 6H, -N-CH 2 -), 2.79 (t, 6H, -C arom. -CH 2 -), 2.65 (t,

6H, -S-CH 2 -CH 2 O-), 2.59 - 2.44 (m, 12H, -N- (CH 2 ) 2 -CH 2 -, O = C-CH 2 -), 1.87 (p, 6H,

-N-CH 2 -CH 2 -CH 2 -), 1.35 (s, 54H, -CH 3 ).

13 C NMR (76 MHz, CDCI 3 ) d = 173.08, 152.31, 149.09, 136.08, 131.10, 124.91,

63.41, 42.32, 36.50, 34.45, 31.08, 30.47, 29.64, 27.61.

According to scheme 3

Scheme 3

5.20 g (20.86 mmol, 1 eq) of triallyl isocyanurate with 11.08 g (141.85 mmol, 6.8 eq) of 2-mercaptoethanol are dissolved in a 50 ml Schlenk flask with septum with stirring and homogenized. The clear solution is with N2 for 1 h

degassed. Under N2 the septum is exchanged for a reflux condenser with bubble counter and the solution is heated to 105 ° C. After reaching

16 mg of dicumyl peroxide are added to the temperature and the reaction mixture is stirred at 105 ° C. for 8 h. The reaction is controlled via

1H NMR analysis by decreasing the C = C double bonds. The clear solution

excess thiol is removed at 80 ° C. under vacuum (10 -2 mbar)

and cleaned up. A transparent gel of 9.97 g (97% of theory) remains.

According to scheme 4

Scheme 4

7.65 g (15.82 mmol, 1 eq) of the thioether precursor are added

15.51 g (53.04 mmol, 3.35 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Metilox) in a 100 ml Schlenk flask with condensation bridge and cold trap with vacuum connection under N 2 at 80 ° C melted and homogenized. The clear melt under N 2

156.83 mg (4.93 mmol, 0.31 eq) DBTO added and the temperature up

140 ° C increased. A slight vacuum of ~ 200 mbar is applied and the reaction mixture is stirred for 5 h. After the end of the reaction, the

Pressure reduced to 10 -3 mbar, the temperature increased to 160 ° C and excess Metilox condensed. After gassing with N 2 , the transparent reaction melt is cooled to RT and then taken up in dichloromethane. 1.4 g of acid-activated are stirred

Bleaching earth (Optimum 210 FF, Clariant) added and the suspension for 30

min refluxed. It is filtered through a short silica pad and the solvent

removed under vacuum. A glass-like, transparent solid remainsof 16.86 g (83% of theory). The structure was confirmed by its 1H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) d = 6.91 (s, 6H, -Carom.-H), 5.00 (s, 3H, -Carom.-OH), 4.15 (t, 6H, -COOCH2-), 3.92 (t, 6H, -N-CH 2 -), 2.79 (t, 6H, -C arom. -CH 2 -), 2.65 (t, 6H, -S- CH 2 -CH 2 O-), 2.60 - 2.37 (m, 12H, -N- (CH 2 ) 2 -CH 2 -, O = C-CH 2 -), 1.87 (p, 6H, -N-CH 2 -CH 2 -CH 2 -), 1.35 ( s, 54H, -CH 3 ).

13 C NMR (76 MHz, chloroform-d) d = 172.98, 152.20, 148.98, 135.97, 130.99, 124.80, 63.29, 42.20, 36.38, 34.33, 30.95, 30.34, 29.52, 27.49 ppm.

b) Synthesis of Example B According to the Invention:

illustration 1

Analogously to Example A Scheme 1, 5.00 g (0.020 mol, 1 eq) of triallyl cyanurate with 4.78 g (0.061 mol, 3.05 eq) of 2-mercaptoethanol with an exposure time of 50 min. implemented. Purification takes place under high vacuum at 60 ° C.

9.1 g (94% of theory) of a transparent, pale yellow and medium-viscosity gel are obtained.

Analogously to Example A Scheme 2, 4 g (0.080 mol, 1 eq) of the thioether are added

7.74 g (0.026 mol, 3.25 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate were reacted at ~ 100 mbar and worked up with water. A hard, yellow-transparent solid remains. The yield is 9.20 g(88% of theory). The structure of Figure 1 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, CDCl 3 ) d = 6.91 (s, 6H, -C arom. -H), 5.00 (s, 3H, -C arom. -OH), 4.14 (t, 6H, -COOCH 2 - ), 3.91 (t, 6H, -OCH 2 -), 2.79 (t, 6H, -C arom. -CH 2 -), 2.65 (t, 6H, -S-CH 2 -CH 2 O-), 2.58 - 2.47 (m, 12H, -S-CH 2 - (CH 2) 2 O-, O = C-CH 2 -), 1.87 (p, 6H, -O-CH 2 -CH 2 -CH 2 -), 1.35 (s, 54H, -CH 3 ).

13 C NMR (76 MHz, CDCI 3 ) d = 172.97, 152.20, 135.97, 130.99, 124.80, 63.30, 42.21, 36.39, 34.34, 30.97, 30.36, 29.52, 27.50.

Analogously to Example A Scheme 3, 5.21 g (20.90 mmol, 1 eq) of triallyl cyanurate are reacted with 7.97 g (102.01 mmol, 4.88 eq) of 2-mercaptoethanol at a reaction temperature of 110 ° C. within a reaction time of 31 H. The purification is carried out under high vacuum at 100 ° C. A transparent gel of 9.01 g (89% of theory) remains.

Analogously to Example A Scheme 4, 9.00 g (18.61 mmol, 1 eq) of the thioether with 22.40 g (76.60 mmol, 4.12 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 50-200 mbar implemented and cleaned as described with 2.8 g of bleaching earth. The yield of the glassy, ​​transparent and highly viscous resin is 14.27 g (61% of theory). The structure of Figure 1 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) δ = 6.91 (s, 6H, -C arom. -H), 5.00 (s, 3H, -C arom. -OH), 4.40 (t, 6H, -C arom -O-CH 2 -), 4.16 (t, 6H, -COOCH 2 -), 2.79 (t, 6H-C arom. -CH 2 -), 2.65 (td, 12H, -CH 2 -S-CH 2 ) , 2.57 - 2.50 (m, 6H, O = C-CH 2 -), 1.99 (p, 6H, -O-CH 2 -CH 2 -CH 2 -), 1.35 (s, 54H, -CH 3 ) ppm.

13 C NMR (76 MHz, chloroform-d) δ = 173.01, 172.98, 152.20, 135.97, 130.98, 124.80, 66.73, 63.33, 36.37, 34.33, 30.96, 30.50, 30.34, 28.64 ppm.

c) Synthesis of Example C According to the Invention:

Figure 2

Analogously to Example A Scheme 1, 7.0 g (0.028 mol, 1 eq) of tetraallyloxyethane are reacted with 8.8 g (0.113 mol, 4.1 eq) of 2-mercaptoethanol. The exposure time is 60 min. After aqueous work-up as in Example A, the mixture is further purified under high vacuum at 80 ° C. and freed from the solvent. 13.6 g (87% of theory) of a transparent, amber-colored and low-viscosity gel are obtained.

Analogously to Example A Scheme 2, 3.52 g (0.006 mol, 1 eq) of the thioether with 7.72 g (0.025 mol, 4.0 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 140 ° C and ~ 80 mbar implemented. The crude product is dissolved in about 200 ml of ethyl acetate and worked up in water analogously to Example A. 9.25 g (92% of theory) of a transparent, amber-colored and highly viscous gel are obtained. The structure shown in Figure 2 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, CDCl 3 ) d = 6.91 (s, 8H, -C arom. -H), 5.00 (s, 4H, -C arom. -OH), 4.25 (s, 2H, -CH-CH -), 4.15 (t, 8H, -COOCH 2 -), 3.76 - 3.46 (m, 8H, -CH-O-CH 2 ), 2.79 (t, 8H, -C arom. -CH 2 -), 2.64 ( t, 8H, O = C-CH 2 -) 2.70 - 2.42 (m, 16H, -CH 2 -S-CH 2 -), 1.79 (p, 8H, -S-CH 2 -CH 2 -CH 2 -O -), 1.35 (s, 72H, -CH 3 ).

13 C NMR (76 MHz, CDCl 3 ) d = 172.97, 152.19, 135.94, 130.99, 124.79, 102.37, 66.01, 63.36, 36.38, 34.33, 30.96, 30.34, 29.84, 28.92.

Analogously to Example A Scheme 3, 5.00 g (19.66 mmol, 1 eq) of tetraallyloxyethane with 7.37 g (94.33 mmol, 4.8 eq) of 2-mercaptoethanol and 216 mg (0.80 mmol, 0.04 eq) of dicumyl peroxide at a reaction temperature of 100 ° C for Stirred for 2 hours. 1.34 g (17.15 mmol, 1.15 eq) of 2-mercaptoethanol are again added and the mixture is stirred for a further 2.5 h. The purification takes place under high vacuum at 100 ° C. A transparent, slightly yellow gel of 10.07 g (90% of theory) remains.

Analogously to Example A Scheme 4, 8.59 g (15.15 mmol, 1 eq) of the thioether with 19.50 g (66.68 mmol, 4.4 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 50-200 implemented mbar and cleaned as described with 2.8 g of bleaching earth. The yield of the glassy, ​​transparent and slightly yellow, highly viscous resin is 14.27 g (61% of theory). The structure shown in Figure 2 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) δ = 6.91 (s, 8H, -C arom. -H), 5.00 (s, 4H, -C arom. -OH), 4.25 (s, 2H, -CH- CH-), 4.15 (t, 8H, -COOCH 2 -), 3.75 - 3.43 (m, 8H, -CH-O-CH 2 ), 2.80 (t, 8H, -C arom. -CH 2 -), 2.64 (t, 8H, O = C-CH 2 -), 2.61 - 2.48 (m, 16H, -CH 2 -S-CH 2 -), 1.79 (p, 8H, -S-CH 2 -CH 2 -CH 2 -O-), 1.35 (s, 72H, -CH 3 ) ppm.

13 C NMR (76 MHz, chloroform-d) δ = 172.97, 152.20, 135.95, 131.00, 124.80, 102.38, 66.02, 63.36, 36.38, 34.33, 30.96, 30.35, 29.85, 28.92.

d) Synthesis of Example D According to the Invention:

Figure 3

Analogously to Example A Scheme 1, 5.71 g (0.055 mol, 1 eq) of styrene with 4.71 g (0.060 mol, 1.1 eq) of 2-mercaptoethanol and 0.2 wt.% Phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator based on the styrene) set. The transparent, low-viscosity crude product is taken up in about 100 ml of dichloromethane and worked up in water analogously to Example A. 7.48 g (75% of theory) of a transparent, low-viscosity gel are obtained.

Analogously to Example A Scheme 2, 4.12 g (0.023 mol, 1 eq) of the thioether with 7.72 g (0.025 mol, 1.1 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 140 ° C. and Implemented ~ 800 mbar. The crude product is taken up in about 150 ml of toluene and worked up in water analogously to Example A. 9.27 g (93% of theory) of a transparent, yellowish and highly viscous gel are obtained. The structure of Figure 3 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, CDCI 3 ) d = 7.29 - 7.05 (m, 5H, -C arom., Styrene -H), 6.91 (s, 2H, -C arom., Metilox -H), 4.99 (s, 1H, -C arom., Metilox -OH), 4.15 (t, 2H, COOCH 2 -), 2.86 - 2.68

(m, 6H, -CH 2 -S-CH 2 -CH 2 -), 2.65 (t, 2H, C arom., Metiiox -CH 2 -), 2.59 - 2.46 (m, 2H,

O = C-CH 2 -), 1.35 (s, 18H, -CH 3 ).

13 C NMR (76 MHz, CDCI 3 ) δ = 140.23, 128.63, 128.54, 128.50, 128.35,

126.49, 125.85, 60.30, 36.37, 35.50, 33.22.

e) Synthesis of Example E According to the Invention:

Figure 4

Analogously to Example A Scheme 1, 6.00 g (0.037 mol, 1 eq) of trivinylcyclo-hexane with 8.81 g (0.113 mol, 3.05 eq) of 2-mercaptoethanol with 0.2 wt% phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide ( Photoinitiator based on the

Trivinylcyclohexan) implemented. The transparent, medium-viscosity and pale yellow crude product is taken up in about 100 ml of diethyl ether and worked up in water analogously to Example A. After further purification under high vacuum at 80 ° C, 13.8 g (94% of theory) of a transparent, pale yellow and medium-viscosity gel are obtained.

Analogously to Example A Scheme 2, 4.00 g (0.010 mol, 1 eq) of the thioether with 8.99 g (0.031 mol, 3.05 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 150 ° C. and implemented at ~ 100 mbar. The purification is carried out analogously to Example A. A tough, yellow-transparent resin remains with a yield of 10.21 g (86% of theory). The structure of Figure 4 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, CDCI 3 ) δ = 6.91 (s, 6H, C arom. -H), 5.00 (s, 3H, -C arom. -OH), 4.15 (t, 6H, -COOCH 2 -) , 2.90 - 2.73 (t, 6H, -C arom. -CH 2 ), 2.64 (t, 6H, O = C-CH 2 -), 2.60 - 2.31 (m, 12H, -CH 2 -S-CH 2 - ), 1.35 (s, 54H, -CH 3 ), 1.99 - 0.38 (m, 15H, -CH 2 -CH ring, aliph., CH 2 , ring, aliph. ).

13 C NMR (76 MHz, CDCI 3 ) d = 173.00, 152.20, 135.97, 131.01, 124.81, 63.45, 40.71, 38.44, 37.07, 36.61, 36.42, 34.35, 33.28, 32.39, 31.00, 30.61, 30.38, 29.91, 29.54.

f) Synthesis of Example F According to the Invention:

Figure 5

Analogously to Example A Scheme 1, 6.12 g (0.025 mol, 1 eq) of diallyl phthalate with 4.08 g (0.052 mol, 2.1 eq) of 2-mercaptoethanol with 0.2 wt.% Phenyl-bis (2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator , based on the diallyl phthalate) implemented. Purification takes place under high vacuum at 60 ° C. 9.91 g (99% of theory) of a transparent, yellowish and low-viscosity gel are obtained.

Analogously to Example A Scheme 2, 3.50 g (0.009 mol, 1 eq) of the thioether with 5.09 g (0.174 mol, 2.0 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 140 ° C and implemented at ~ 800 mbar. Purification takes place under high vacuum at 140 ° C. 7.38 g (74% of theory) of a transparent, yellowish and low-viscosity gel are obtained. The structure of Figure 5 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, CDCI 3 ) d = 7.64 (m, 2H, -CC arom., Phthalate -H), 7.55 - 7.37 (m, 2H, -C arom., Phthalate - H), (s, 4H , -C arom., Metilox -H), 5 . 00 (s, 2H, -C arom . -OH), 4.44 -4.28 (m, 4H, -C arom., Phthalate -COOCH 2 -), 4.22 - 4.04 (m, 4H, -CH 2 COOCH 2 -), 2.79 (t, 6H, -C aroma. -CH 2 -), 2.70 - 2.48 (m, 12H), 1.96 (p, 4H, -S-CH 2 -CH 2 -CH 2 -), 1.35 (s, 36H , -CH 3 ).

13 C NMR (76 MHz, CDCI 3 ) δ = 172.97, 167.40, 152.19, 135.95, 131.99, 131.14, 130.97, 128.91, 124.79, 64.12, 63.33, 62.83, 36.37, 34.32, 30.95, 30.48, 30.34, 28.74, 28.67.

Analogously to Example A Scheme 3, 9.18 g (37.28 mmol, 1 eq) of diallyl phthalate with 6.99 g (89.47 mmol, 2.4 eq) of 2-mercaptoethanol and 180 mg (1.1 mmol, 0.02 eq) of 2,2'-azobis (2-methylpropionitrile) stirred at a reaction temperature of 70 ° C for 1 h. Another 0.04 g (0.24 mmol, 0.006 eq) of 2,2'-azobis (2-methylpropionitrile) are added and the mixture is stirred at 80 ° C. for a further 9 h. Purification takes place under high vacuum at 80 ° C. A trans-parent, slightly yellow, low-viscosity gel of 13.68 g (91% of theory) remains.

Analogously to Example A Scheme 4, 8.72 g (21.66 mmol, 1 eq) of the thioether with 12.99 g (44.42 mmol, 2.05 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 50-200 mbar implemented and cleaned as described with 1.4 g of bleaching earth. The yield of the transparent and slightly yellow, highly viscous resin is 8.77 g (87% of theory). The structure after

Figure 5 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) δ = 7.72 - 7.60 (m, 2H, -CC arom., Phthalate -H), 7.53 - 7.39 (m, 2H, -C arom., Phthalate -H), 6.92 (s, 4H, -C aroma., Metilox -H), 5.00 (s, 2H, - C aroma. -OH), 4.35 (t, 4H, -C aroma., phthalate -COOCH 2 -), 3.66 (t , 4H, -CH 2 COOCH 2 -), 2.80 (t, 4H, C arom. -CH 2 -), 2.64 - 2.49 (m, 8H, -CH 2 -S-CH 2 ), 1.97 (p, 4H, -S-CH 2 -CH 2 - CH 2 -), 1.36 (s, 36H, -CH 3 ).

g) Synthesis of Example G According to the Invention:

According to scheme 5

Scheme 5

5.40 g (35.03 mmol, 1 eq) of N, N'-methylenebisacrylamide are stirred with 12.21 g (156.28 mmol, 4.5 eq) of 2-mercaptoethanol and 370 mg (3.6 mmol, 0.1 eq) of triethylamine in 20 ml of methanol and suspended. The heating clarifies homogeneously and transparently when heated, whereby a white solid precipitates after a few minutes. The solid is filtered off, washed three times with 15 ml of distilled water and 15 ml of methanol and dried in a drying cabinet. A white solid of 7.40 g (68% of theory) remains.

Figure 6

Analogously to Example A Scheme 4, 6.95 g (22.38 mol, 1 eq) of the thioether with 31.30 g (107.04 mol, 4.8 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 160 ° C and 50-200 mbar implemented within 8 hours. Purification is carried out as described with 1.4 g of bleaching earth. 16.72 g (90% of theory) of a glassy, ​​light brown solid are obtained. The structure according to Figure 6 was confirmed by its 1 H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) δ = 6.91 (s, 4H, -C arom . -H ), 6.87 (t, 2H, -NH- CH 2 -NH-), 5.02 (s, 2H, - C aroma -OH), 4.54 (t, 2H, -NH-CH 2 -NH-), 4.15 (t, 4H, -C aroma. _ COOCH 2 -), 2.86 - 2.73 (m, 8H, -NH- CO-CH 2 -, -C aroma. -CH 2 -CH 2 -), 2.54 (t, 4H, - C aroma. - CH 2 ) 2.39 (t, 4H, C aroma -CH 2 -), 1.35 (s , 36H, -CH 3 ).

13 C NMR (76 MHz, chloroform-d) δ = 173.06, 172.06, 152.21, 136.01, 130.96, 124.80, 63.37, 44.67, 36.42, 36.37, 34.33, 30.94, 30.74, 30.35, 27.67 ppm.

h) Synthesis of Example H According to the Invention:

Figure 7

Analogously to Example A Scheme 1, 6.64 g (21.53 mol, 1 eq) o, o'- diallylbisphenol A with 3.45 g (44.16 mol, 2.05 eq) 2-mercaptoethanol with 0.1 wt.% Phenyl-bis (2,4,6- trimethylbenzoyl) phosphine oxide (photoinitiator, based on the diallyl). Purification takes place under high vacuum at 60 ° C. 9.04 g (90% of theory) of a transparent, yellowish and low-viscosity gel are obtained.

Analogously to Example A Scheme 2, 3.25 g (6.99 mol, 1 eq) of the thioether with 4.29 g (14.69 mol, 2.1 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 145 ° C and 50-200 mbar implemented within 5 h. The

Purification takes place under high vacuum at 150 ° C. 6.07 g (88% of theory) of a transparent, yellowish and highly viscous resin are obtained. The structure according to Figure 7 was confirmed by its 1H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) δ = 6.91 (s, 4H, -C arom. -CH), 6.87 - 6.70 (m,

4H, -CH 2 -C bisphenol -CH 2 ), 6.57 (s, 2H, C bisphenol OH CH 2 -), 5.15 (S, 2H, C bisphenol - OH), 5.00 (s, 2H, -C aroma. - OH), 4.14 (t, 4H, -COO-CH 2 -CH 2 -S-), 2.80 (t, 4H, -C aroma - CH 2 -CH 2 -COO-), 2.68 - 2.50 (m, 12H) , 2.46 (t, 4H, -C aroma. -CH 2 -CH 2 -COO-), 1.80 (p,

4H,, -S-CH 2 -CH 2 -CH 2 -), 1.52 (s, 6H, -C bisphenol H 3 ), 1.35 (s, 36H, -CH 3 ).

13 C NMR (76 MHz, chloroform-d) δ = 173.29, 152.22, 151.57, 143.31, 135.98, 130.97, 128.84, 126.45, 125.64, 114.97, 63.53, 41.66, 36.40, 34.33, 31.69, 30.95, 28.93.

i) Synthesis of Example I According to the Invention:

Figure 8

Analogously to Example A Scheme 3, 5.56 g (19.08 mmol, 1 eq) of trimethylallyl isocyanurate with 9.63 g (123.26 mmol, 6.46 eq) of 2-mercaptoethanol and

160 mg (0.60 mmol, 0.03 eq) of dicumyl peroxide were stirred at a reaction temperature of 115 ° C. for 8 h. Purification takes place under high vacuum at 80

° C. A transparent, slightly yellow gel of 7.14 g (71% of theory) remains.

Analogously to Example A Scheme 4, 7.00 g (13.31 mmol, 1 eq) of the thioether with 16.24 g (55.54 mmol, 4.2 eq) of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate at 50-200 implemented mbar and cleaned as described with 2.8 g of bleaching earth. The yield of the glassy, ​​transparent and slightly orange, glassy solid is 16.29 g (94% of theory). The structure of Figure 8 was confirmed by its 1H NMR spectrum.

1 H NMR (300 MHz, chloroform-d) d = 6.91 (s, 6H, -C arom . -CH), 5.00 (s, 3H, -C arom . -OH), 4.12 (t, 6H, -COO- CH 2 -CH 2 - S -), 3.89 (dd, 3H, -N-CH 2 '-), 3.73 (dd, 3H, -N-CH 2 "-), 2.79 (t, 6H, -C aroma . -CH 2 -), 2.63 (t, 6H, -COO-CH 2 -CH 2 -S-),

2.53 (m, 9H, -C aroma. -CH 2 -CH 2 -, -S-CH 2 -CH-), 2.41 (dd, 3H, -S-CH 2 "-CH-). 2.18 (p, 3H, -N-CH 2 - CH-), 1.35 (s, 54H, -CH 3 ), 0.95 (d, 9H, -CH-CH 3 ).

i) Synthesis of Polymeric Example J According to the Invention:

In a heated 100 mL Schlenk flask, 20.88 (83.76 mmol, 1 eq) triallyl isocyanurate are dissolved in 6.66 g (85.24 mmol, 0.98 eq) 2-mercaptoethanol. The reaction mixture is degassed twice using the Freeze Pump Thaw method. After the addition of a spatula tip of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide (photoinitiator), the reaction mixture is irradiated with UV light with a wavelength of 366 nm for 1 h. A significant increase in the viscosity of the reaction mixture must be observed after half an hour. The reaction mixture is then heated to 110 ° C. and 0.1 ml of 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane (radical initiator) are added. After a reaction time of 2 h, a further 1 ml of 2,5-dimethyl-2,5-di- (tert-butylperoxy) -hexane is added. The viscous, slightly yellow reaction mixture is precipitated in 250 ml of cold methanol after a reaction time of 17 h. After drying under high vacuum, 3.80 g of a colorless, powdery product are obtained.

2.76 g of the polymeric thioether and 16.16 g of methyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are dissolved in 40 ml of chloroform in a 100 mL Schlenk flask. The solution is heated to 100 ° C. under reflux and 100 mg of dibutyltin oxide are added. After 26 h the reaction mixture is cooled to room temperature and poured into 300 ml of cold methanol.

pours. The product which precipitates is filtered off, washed with methanol and then dried under high vacuum. 2.02 g of the white, powdery product are obtained. The polymeric compound was confirmed via its FTIR spectrum.

IR: 3521 v (-OH), 2953 v (-CH 2 ), 1670 v (-C ester = O), 1155 v (para subst.aromatic), 1450 v (-CN), 931 v (= CH), 762 v (-CS-), 697 v (= CH mono-substituted benzene) cm -1 .

III. Application testing of the examples according to the invention

a) Application test of example A according to the invention

Example A according to the invention was incorporated with the weight percentages shown in Table 1 in polypropylene (Moplen HP 500N, Lyondell Basell Industries) in comparison with a commercially available sulfur-containing phenolic antioxidant (Comparative Example 2, Songnox 1035, Songwon). Example 1 according to the invention shows the comparable weight concentration to the comparative example, Example 2 according to the invention was calculated according to the molar equivalent of phenolic antioxidant groups.

Table 1: Compositions of the examples and comparative examples according to the invention

Songnox 1035 means the following structure: 2,2'-thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]

DSTDP: distearyl thiodipropionate

DLDTP: dilauryl dithiopropionate

The compound mixtures were extruded in a double-screw

Process 11 (Fisher Scientific) type extruders under the temperature profile shown in Table 2. The polymer melt is discharged at 200 rpm and cooled in a water bath and then granulated. Table 2: Temperature profile of the extrusion tests

The granules were aged in accordance with DIN EN ISO 4577: 1999 in a forced air oven at 150 ° C. and 50% air circulation for 80 days and samples were taken after 5, 10 and 50 days. The residual stability was then assessed by static OIT measurement (Oxidative Induction Time) according to DIN EN ISO 11357-6: 2013 with synthetic air as the purge gas at 230 ° C or 210 ° C. Table 3 contains the induction times determined. The longer the induction time, the higher the residual stability of the polymer.

Table 3: OIT values ​​after aging at 150 ° C

In the case of unstabilized polypropylene (comparative example 1), the oxidation begins in a very short time; after aging there is no residual stability at all. The compounds with added antioxidants, delayedthe beginning of the oxidation. Surprisingly, the examples according to the invention show a superior stability of the stabilizer according to the invention compared to the comparative examples.

According to Table 4, measurements of the yellowness index (Spectro-guide sphere gloss with white standard, BYK Additives & Instruments) of the up to 80 days aged and unaged samples showed a significantly lower tendency to discolouration of the examples according to the invention in contrast to the comparative examples.

Table 4: Yellowness index after aging at 150 ° C.

b) Application test of example C according to the invention

The melt volume flow rate of the aged granules was reduced

DIN EN ISO 1133-2: 2011 determined (2.16 kg, 230 ° C).

Table 5: Compositions of the examples and comparative examples according to the invention

Table 6 contains the melt volume flow rates determined. The lower the stability of the polymer, the higher the melt volume flow rate.

Table 6: Melt volume flow rate after aging at 150 ° C

In the case of unstabilized polypropylene (comparative example 1), the chain breakdown of the polypropylene takes place in a very short time; after aging there is no residual stability at all. As a result, the MVR measured values ​​can no longer be measured, since a strong reduction and thus very high MVR values ​​(> 500) are achieved. The compounds with added antioxidants delayed the start of chain degradation. The example according to the invention surprisingly shows a superior stability of the stabilizer according to the invention over the course of aging compared to the comparative examples.

c) Application test of the examples according to the invention in talc-filled polypropylene

The test was carried out analogously to the application test of Example A according to the invention

Assessment of the stability by static OIT measurement for the examples according to the invention and comparative examples in

Table 7 with the addition of talc as a filler at 230 ° C without aging. The percentage of stabilizer added relates to the polypropylene content.

Table 7: Compositions of the examples according to the invention and comparative examples in Finntalc M15 filled polypropylene (all figures in% by weight).

Table 8: OIT values ​​in PP with 20% by weight Finntalc M15 before aging at 230 ° C.

For unstabilized polypropylene (comparative example 5) with Finntalc

M15 filler, the oxidation begins immediately after switching from an inert atmosphere to an oxygen-containing atmosphere, so that there is no residual stability at all. The examples according to the invention show a clearly superior stability of the stabilizers according to the invention compared to the comparative examples.

Analogously, the stabilizers according to the invention were incorporated into 10% talc of the Luzenac 1445 type according to Table 9 and the OIT was determined (Table 10).

Table 9: Compositions of the examples according to the invention and comparative examples in polypropylene filled with Luzenac 1445 (all figures in% by weight).

Table 10: OIT values ​​in PP with 10 wt.% Luzenac 1445 before aging.

In the case of unstabilized polypropylene (comparative example 7) with the Luzenac 1445 filler, the oxidation begins very early. The examples according to the invention show a clearly superior stability of the stabilizers according to the invention compared to the comparative examples, even at a comparatively lower concentration (examples 9, 12 and 14 according to the invention).

d) application testing of the examples according to the invention in further

Systems

Compound A according to the invention was also incorporated in a concentration of 0.3% in the following polymers:

D1: acrylonitrile butadiene styrene (ABS)

D2: polyamide-6

D3: polyamide-6 with 30% glass fibers

D4: polybutylene terephthalate

In all cases, improved long-term stability, ie preservation of the mechanical properties, can be demonstrated compared to the polymer.

Claims

1. Compound according to general formula I.

where the variables A, B, D, R, b, x, y, z each independently have the following definition:
A is an aromatic, unsaturated or saturated radical,
BO or NH,
D is a linear or branched aliphatic radical having 1 to 12 carbon atoms,
R is a radical with at least one sterically hindered group and at least one hydroxyl group,
b 0 or 1,
x 0 to 12,
y 1 is 4,
from 1 to 6.
2. Compound according to the preceding claim, characterized in that the variable A is selected from the group consisting of z-valent cyanuric acid residues, where z has the meaning given in claim 1, triazine residues, cyclic aliphatic hydrocarbon residues with 5 to 36 Carbon atoms, in particular cyclohexyl, aromatic hydrocarbon radicals, in particular phenyl, linear or branched aliphatic hydrocarbon radicals with 2 to 36 carbon atoms.
3. Compound according to one of the preceding claims, characterized in that the variable R represents a grouping with at least one sterically hindered hydroxyphenyl radical, in particular has the following meaning
in which
E is the same or different in each occurrence and is a linear aliphatic, branched aliphatic, cycloaliphatic alkyl radical with 1 to 18 carbon atoms, an aromatic radical with 6 to 36 carbon atoms or hydrogen, in particular a tert-butyl group or one Represents methyl group,
a is 1 or 0, and
c is 0, 1, 2, 3, or 4.
4. Connection according to one of the preceding claims, characterized in that the variables x, y and z each independently of one another have the following meaning:
x 0 or 1,
y 1 or 2,
z 1, 2, 3 or 4.
5. Compound according to one of the preceding claims, characterized in that the compound of general formula I is selected from the group consisting of the following compounds:
where Z has the following meaning:

and the variables B, D, R, b, x, y and z are as defined in claim 1.
6. Connection according to one of the preceding claims, characterized in that D is selected from the group consisting of
-CH 2 - or a 1,2,3-propynyl radical.
7. Connection according to one of the preceding claims, selected
from the group of the following compounds:
with each occurrence independently of one another, the radical Y being the
has the following meaning:
o
where in the above radicals the tBu radical can also be wholly or partly substituted by a methyl group and / or hydrogen.
8. Process for the preparation of a compound according to general formula
I according to one of the preceding claims, in which a connection according to general formula II

with a thiol according to one of the general formulas purple or IIIb
is implemented, and in the event that a thiol of the general formula purple was used, then an implementation of the Reaction of the compounds of the formula II and IIIa obtained reaction product with a compound of the general formula IV
in which
X represents a leaving group, and
the meaning of the variables A, B, D, R, b, x, y, z in the compounds of the formulas Ila, IIb and III are as defined in claim 1.
9. The method according to the preceding claim, characterized in that X is an alcoholate, halide, trifluoromethanesulfonate, tosylate, mesylate, fluorosulfonate or nonaflate.
10. The method according to any one of the two preceding claims, characterized in that the reaction of the compound according to general formula II with the thiol according to one of the general formulas IIIa or IIIb with an excess of the thiol, based on the unsaturated function the compound is carried out according to general formula II.
11. Composition containing or consisting of
at least one organic component to be stabilized, and at least one compound according to one of claims 1 to 7.
12. Composition according to the preceding claim, characterized in that the component to be stabilized is selected from the group consisting of plastics, oils, lubricants and greases.
13. Composition according to one of the two preceding claims, containing or consisting of
95.00 to 99.99 parts by weight, preferably 97.00 to 99.95 parts by weight, particularly preferably 98.00 to 99.90 parts by weight of at least one component to be stabilized, and
0.01 to 5.00 parts by weight, preferably 0.05 to 3.00 parts by weight, particularly preferably 0.10 to 2.00 parts by weight of at least one compound according to one of Claims 1 to 7.
14. Composition according to one of claims 11 to 13, characterized in that in addition at least one additive selected from the group consisting of UV absorbers, light stabilizers, stabilizers, antioxidants, hydroxylamines, benzofurans, metal deactivators, filler deactivators, antiozonants , Nucleating agents, impact strength improvers, plasticizers, lubricants, rheology modifiers, thixotropy agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, anti-blocking agents, coupling agents, coupling agents - agents, water repellents, adhesion promoters, dispersants, degradation additives,Defoaming agents, odor scavengers, markers, anti-fogging agents, fillers and reinforcing materials are included.
15. The composition according to any one of claims 11 to 14, characterized in that it additionally contains at least one additive selected from the group consisting of phosphites, phosphonites, hydroxylamines or nitrones.
16. A method for stabilizing an organic component to be stabilized, in particular against oxidative, thermal or actinic degradation or damage, in which at least one compound according to one of Claims 1 to 7 is mixed with or incorporated into the organic component to be stabilized .
17. Use of a compound according to any one of claims 1 to 7 for stabilizing organic materials against oxidative, thermal or actinic degradation or damage.