ITMI992158A1 - STABILIZING COMPOUNDS CONTAINING A STEARICALLY PREVENTED PHENOLIC GROUP AND A SILIC FUNCTION - Google Patents

Description

"STABILIZING COMPOUNDS CONTAINING A STERICALLY IMPEDITED PHENOL GROUP AND A SILICIC FUNCTION"

DESCRIPTION

The present invention relates to stabilizing compounds containing a sterically hindered phenolic group and a silicic function.

More particularly, the present invention relates to stabilizing compounds containing in the molecule a sterically hindered phenolic group and a hydrolysable silica function, the complex resinous structures derived therefrom by hydrolysis and condensation, and their use as stabilizers to the oxidative degradation caused by the heat of organic polymers. .

The present invention also relates to the polymeric compositions stabilized with the aforesaid compounds and the manufactured articles obtained from their processing.

As is known, organic polymers are subject to degradation over time due to exposure to environmental conditions: this degradation manifests itself with the impoverishment of the physical characteristics of the polymers such as, for example, the decrease in the breaking load and flexibility, accompanied by variation of the viscosity index.

To counteract said degradation, as known in the art, small quantities of antioxidant compounds are usually introduced into the organic polymers, such as, for example, spherically hindered phenols.

The problems encountered in the stabilization of organic polymers derive essentially from phenomena of incompatibility between the antioxidant compound and the polymer and from phenomena of release of the antioxidant compound by the polymer itself. In stabilization through known antioxidant compounds, the aforementioned phenomena, albeit to a more or less high degree, always occur and, consequently, the need was felt to have antioxidant compounds that were more compatible with organic polymers and were able to remain stably in the polymers themselves.

In European patents EP 162.523 and EP 182.415 reactive antioxidant compounds are described which contain in the molecule a sterically hindered phenolic group and a hydrolyzable silica function. Said reactive antioxidant compounds can give rise to complex resinous structures, internally or externally to the polymer, or they can chemically bind to the polymer or to a solid support. As a result of these interactions, structures are obtained which on the one hand unexpectedly maintain unchanged the antioxidant characteristics of sterically hindered phenols and on the other hand have characteristics of permanence in the polymer superior to those of the initial reactive antioxidant compounds and to those of the antioxidant compounds known in the art.

The Applicant has now found that some of the aforesaid reactive antioxidant compounds, obtained by suitably selecting the sterically hindered phenolic group, the chain of carbon atoms which binds the sterically hindered phenolic group to the hydrolyzable silica function and the molecular weight range of the complex resinous structures derived from them by hydrolysis and condensation, they give greater stability to the organic polymers to which they are added.

Therefore, the subject of the present invention are stabilizing compounds containing a sterically hindered phenolic group and a hydrolysable silica function having general formula (I):

in which:

R and R ', the same or different from each other, represent a halogen atom such as, for example, chlorine; a linear or branched C1-C4 acyloxy group; a linear or branched C1-C4 alkyloxy group;

as well as stabilizing compounds, consisting of the complex resinous structures derived from the hydrolysis and condensation of the aforementioned stabilizing compounds having general formula (I), having general formula (II):

in which

R1 represents a hydroxyl group;

R2 represents a hydrogen atom;

or, R1 and R2 jointly represent a direct bond giving rise to cyclic structures;

m is an integer between 1 and 2000 inclusive;

n, p and q, each independently, are an integer between 0 and 50 inclusive;

R3 represents a hydrogen atom; or one of the following groups having general formula (IIa), (IIb), (H e) or (IId):

in which p ', q' and n ', each independently, are an integer between 1 and 50 inclusive; m and R3 have the same meanings described above.

The stabilizing compounds having general formula (II) have an average molecular weight between 396 and 756000, preferably between 1000 and 30000, even more preferably between 1500 and 15000.

The stabilizing compounds having general formula (I) object of the present invention can be prepared according to processes known in the art as described, for example, in European patents EP 162.523 and EP 182.415.

A process for the preparation of the stabilizing compounds having general formula (I) object of the present invention comprises the silylation reaction of a spherically hindered phenol having formula (III):

with a silylating agent having general formula (IV):

in which R and R 'have the same meanings described above.

The aforementioned silylation reaction is carried out at a temperature between 0 ° C and 200 ° C, preferably between room temperature (20 ° C-25 ° C) and 120 ° C, using quantities of reagents ranging from the stoichiometric ones to an excess of silylation agent. Said excess usually reaches up to 50%, preferably it is comprised between 2% and 10%.

The silylation reaction is catalyzed by metal catalysts, ultraviolet radiation and radical initiators. Preferred catalysts for this purpose are platinum compounds and platinum complexes with olefins, in particular chloroplatinic acid. In the case of platinum-based catalysts, the concentration of the catalyst, evaluated as metal, can vary from 1 to 200 parts per million, preferably from 5 to 50 parts per million, in the reaction medium.

The aforesaid silylation reaction can be carried out in an inert organic solvent, usually selected from aliphatic, cycloaliphatic or aromatic hydrocarbons, or esters: said solvents are liquid under the conditions in which one operates.

Specific examples of solvents suitable for the purpose are: heptane, cyclohexane, toluene, tetrahydrofuran, dioxane and dimethoxyethane.

The times of the aforesaid silylation reaction depend on the particular reagents used and on the reaction temperature and are generally comprised between 0.5 hours and 10 hours.

At the end of the silylation reaction, any solvent used and any excess of the silylation agent are removed by stripping and the desired stabilizing compound having general formula (I) is recovered from the residue of said stripping by means of the usual techniques such as, for example, example, crystallization and vacuum distillation. However, generally, the high yield and selectivity values of the aforesaid silylation reaction make the separation and purification treatments of the desired final product unnecessary.

The spherically hindered phenol having formula (III) is a slightly yellow solid having a melting point of 41 ° C, which can be obtained by esterification of the corresponding acid with allyl alcohol.

The silylating agents having general formula (IV) are commercially available products.

The stabilizing compounds having general formula (I) thus obtained can hydrolyze, under mild conditions, to the silyl functionality, generating silanol groups, which can be condensed together to form the stabilizing compounds having general formula (II) which are a further object of the present invention.

Said stabilizing compounds having general formula (II), consisting of complex resinous structures such as silicone resins, maintain the stabilizing characteristics of spherically hindered phenols unaltered and have, to a high degree, characteristics of compatibility with organic polymers and extremely low extractability from polymers themselves.

1 / hydrolysis to silyl functionality occurs simply by contact with water or with ambient humidity, at room temperature (20 ° C-25 ° C) or at a temperature above or below room temperature.

The condensation between the silanol groups, to give the stabilizing compounds having general formula (II), can be catalyzed by acidic or basic agents, by soaps or by metal esters as well as by organo-metal compounds, preferably by compounds based on lead or pond. Preferred catalysts for this purpose are lead naphthenate, dibutyl tin laurate and tin dibutyl diacetate.

Conveniently, the aforesaid catalysts are used in quantities ranging from 0.1% to 10% by weight with respect to the stabilizing compound having general formula (I) subjected to condensation, preferably between 0.2% and 3% by weight.

The above condensation reaction can be carried out at room temperature (20 ° C-25 ° C), as well as at temperatures below or above said room temperature.

The stabilizing compounds having general formula (II) thus obtained can be introduced into the organic polymers to be stabilized by means of the usual techniques used for the purpose.

As regards the stabilizing compounds having general formula (I), said compounds can be introduced directly into the organic polymer to be stabilized within which the hydrolysis reactions to the silicic functionality and interaction between the silanol groups occur spontaneously, obtaining the stabilized polymeric composition.

According to a further embodiment, the hydrolysis of the silica functionality and a partial condensation of the hydrolysis product thus obtained are carried out externally to the organic polymer to stabilize. The product of the partial condensation is then introduced into the organic polymer to be stabilized within which the completion of the condensation takes place, obtaining the complex resinous structures having general formula (II) further object of the present invention.

According to a further embodiment, the stabilizing compounds having general formula (I) object of the present invention are coresinified with conventional silicone paints. Generally, co-resinification requires firing treatment at relatively high temperatures. The materials thus obtained are complex resins in which the stabilizing compound is one of the constituent elements. These materials are generally transparent and hard glass which can be ground to give a powder with an average particle size of 1 μπι or less. In this form, the stabilizing compound can be distributed and homogenized in the polymer to be stabilized in the pigmentary form. The structure of said resinification products essentially depends on the number of groups hydrolyzable to the silicic function of the stabilizing compounds having general formula (I).

Finally, the stabilizing compounds having general formula (I) can be fixed to a solid support containing surface hydroxyl groups. Suitable supports for this purpose are siliceous materials of both natural and synthetic origin such as, for example, diatomaceous earth, celite, silica gel, cement, glass, glass fibers, and silicon aluminates in general. Preferably, the common type of silica known as "fumed-silica" is used which, together with good optical characteristics, has a low apparent density, a high specific surface (generally higher than 200 m <2> / g) and a high surface concentration. of hydroxyl groups.

The bond to the support occurs by reaction of the stabilizing compound having general formula (I), in its hydrolyzed form, with the surface hydroxyl groups of the support. In practice, the support, in the form of powders or granules, is placed in contact with a solution of the stabilizing compound having general formula (I), in an inert organic solvent such as, for example, an aliphatic, cycloaliphatic or aromatic hydrocarbon, or a ether. It also operates in the liquid phase, at a temperature between room temperature (20 ° C-25 ° C) and about 100 ° C and in a time between 0.5 hours and 10 hours, obtaining the hydrolysis of the stabilizing compound having general formula (I) and its bond to the support.

The compound having general formula (I) thus supported is added to the organic polymer to be stabilized by the usual techniques. Said embodiment has the further advantage relating to an optimal distribution of the antioxidant in the polymer.

According to a further embodiment, the stabilizing compounds having general formula (I) are chemically bonded to the organic polymer to be stabilized. Said technique is particularly effective in the case of low molecular weight diolefin polymers or copolymers. The reaction between the stabilizing compound having general formula (I) and the organic polymer to be stabilized generally takes place at a temperature between room temperature (20 ° C-25 ° C) and about 100 ° C, in the presence of an organic solvent inert and in a time between 0.5 and 10 hours.

As stated above, the stabilizing compounds having general formula (I) and (II) object of the present invention are added as antioxidants to the organic polymers. Examples of organic polymers to which they can be added are:

1. Polymers of monoolefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene; as well as cycloolefin polymers such as, for example, cyclopentene or norbornene; polyethylene (which can optionally be cross-linked) such as, for example, high density polyethylene (HDPE), high density and high molecular weight polyethylene ((HDPE-HMW), high density and very high molecular weight polyethylene ("ultrahigh molecular weight ") (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE), (VLDPE), (ULDPE) .

Polyolefins such as, for example the monolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be prepared by various methods known in the literature, preferably by using the following methods:

(a) radical polymerization (generally carried out at high pressure and high temperature);

(b) catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. Said metals generally have one or more ligands such as, for example, oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls which can be π- or σcoordinated. These metal complexes can be in free form or supported on substrates such as, for example, activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. Said catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements belonging to groups la, 11a and / or Illa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amino or silyl ether groups. Said catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (Du-Pont), metallocene or "single site catalyst" (SSC).

2. Mixtures of the polymers described in point (1) such as, for example, mixtures of polypropylene with polyisobutylene; blends of polypropylene with polyethylene (for example, PP / HDPE, PP / LDPE); mixtures of different types of polyethylene (for example, LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene / but- 1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / isoprene copolymers, isobutylene / isoprene copolymers / alkyl acrylate, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethylideneenorbornene; and also mixtures of said copolymers with each other or with the polymers listed above in point (1) such as, for example, polypropylene / ethylene / propylene copolymers, LDPE / ethylene / vinyl acetate copolymers (ÈVA), LDPE / ethylene / acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or "random" polyalkylene / carbon monoxide copolymers and their mixtures with other polymers such as, for example, polyamides.

4. Hydrocarbon resins (for example, C5-C9) comprising their hydrogenated modifications (for example, tackifying resins) and blends with polyalkylenes and starch.

5. Polystyrene, poly (p-methylstyrene), poly (αmethylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures, having a high breaking load, between styrene copolymers and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethylene / propylene / diene terpolymer, styrene block copolymers such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or amethylstyrene such as, for example, styrene in polybutadiene, styrene in polybutadiene / styrene or polybutadiene / acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile and methyl methacrylate in polybutadiene; styrene and maleic anhydride in polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; styrene and maleimide in polybutadiene; styrene and alkyl acrylates or alkyl methacrylates in polybutadiene; styrene and acrylonitrile in ethylene / propylene / diene terpolymers, styrene and acrylonitrile in polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers, as well as mixtures of the copolymers listed above with the copolymers listed in point (6) such as, for example , blends of copolymers known as ABS, MBS, ASA or AES;

8. Polymers containing halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or brominated isobutylene-isoprene copolymers ("halobutyl rubber"), chlorinated polyethylene or chlorosulfonated, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular polymers of halogen-containing vinyl compounds such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride or polyvinylidene fluoride; and also their copolymers such as, for example, vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride vinyl acetate.

9. Polymers derived from α, β-unsaturated acids and their derivatives such as, for example, polyacrylates and polymethacrylates, polymethyl methacrylates, impact modified with butyl acrylate, polyacrylamides and polyacrylonitriles.

10. Copolymers of the monomers referred to in point (9) with each other or with other unsaturated monomers such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate copolymers or acrylonitrile / acrylonitrile / vinyl halide copolymers alkyl methacrylate / butadiene.

11. Polymers derived from unsaturated alcohols and animins, or their acyl or acetal derivatives such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with the olefins referred to in point (1).

12. Homopolymers and copolymers of open chain ethers or of cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers.

13. Polyacetals such as, for example, polyoxymethylene and those polyoxymethylenes which contain comonomers, for example, ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulphides and their mixtures with styrenic polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as the precursors of the above compounds.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4 / 6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and with or without an elastomer as modifying agent, for example, poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforesaid polyamides with polyolefins, olefin copolymers, ionomers or elastomers chemically bonded or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide System").

17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins, and polybenzoimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4dimethylolcyclohexane terephthalate, polyhydroxybenzoates, as well as polyether esters derived from polyethers with groups hydroxyl terminates; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyethersulfones and polyetherketones.

21. Cross-linked polymers derived from aldehydes on the one hand and from phenols, urea and melamines on the other such as, for example, phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins. 22. Dried or non-dried alkyd resins.

23. Resins based on unsaturated polyesters derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also the above resins containing halogens and having good flame resistance.

24. Crosslinkable acrylic resins derived from substituted acrylates such as, for example, epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, resins based on polyester or acrylate resins cross-linked with melamine resins, resins based on urea, resins based on isocyanates, resins based on isocyanates, resins based on polyisocyanates or epoxy resins.

26. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds such as, for example, products of diglycidyl ethers of bisphenol A and bisphenol F, which are cross-linked with the usual cross-linking agents such as, for example, anhydrides or amines, in the presence or absence of accelerators.

27. Natural polymers such as, for example, cellulose, natural rubber, gelatin, and their chemically modified derivatives to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose ; as well as hydrocarbon resins ("rosins") and their derivatives.

28. Blends of the above mentioned polymers ("polyblends") such as, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA , PC / PBT, PVC / CPE, PVC / acrylates, POM / PUR thermoplastics, PC / PUR thermoplastics, POM / acrylates, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS, PBT / PET / PC.

29. Natural or synthetic organic materials which are pure monomer compounds or mixtures of these compounds such as, for example, mineral oils, oils, animal or vegetable fats or waxes, oils, fats or waxes based on synthetic esters (for example, phthalates, adipates, phosphates, trimellitates), as well as mixtures of synthetic esters with mineral oils in any weight ratio, in particular those used in the compositions for spinning, as well as the aqueous emulsions of said organic materials.

30. Aqueous emulsions of natural or synthetic rubber such as, for example, natural latex or latex based on carboxylated styrene-butadiene copolymers.

The stabilizing compounds having general formula (I) and (II) object of the present invention are particularly useful in the stabilization of the organic polymers selected from those reported above. Preferably, they are useful in the stabilization of the polyolefins mentioned above in point (1), in particular of the cross-linked polyolefins and of the polyolefins obtained by catalytic polymerization. Said compounds have proved to be particularly useful in the stabilization of the polyolefins obtained by catalytic polymerization using, as a catalytic system, metallocene or "single site catalyst": in this case, their silicone structure can also contribute to an improvement in processability. The polyolefins stabilized with the compounds having general formula (I) or (II) object of the present invention are particularly useful as insulating material for electric wires, for cables, for pipes.

The present invention also relates to polymeric compositions containing an organic polymer and an effective amount of one or more stabilizing compounds having general formula (I) or (II).

A further object of the present invention are the manufactured articles obtained from the processing of the aforesaid polymeric compositions.

The stabilizing compounds having general formula (I) and (II) object of the present invention are added to the organic polymers to be stabilized in quantities ranging from 0.01% to 5% of the total weight of the polymer to be stabilized, preferably 0.05% and 3 %, even more preferably between 0.1% and 1%.

Said stabilizing compounds can be used as such or in combination with other conventional additives. Said additives are added in quantities ranging from about 0.1% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably between about 0.5% and about 3% by weight. By way of example, some of the additives used are listed below.

1. Antioxidants

1.1 Alkylated monophenols such as, for example: 2,6-dit-butyl-4-methylphenol; 2-t-butyl-4,6-dimethylphenol; 2.6-di-t-butyl-4-ethylphenol; 2,6-di-t-butyl-4-n-butylphenol; 2,6-di-t-butyl-4-isobutylphenol; 2,6-dicyclopentyl-4-methylphenol; 2- (α-methylcyclohexyl) -4.6-dimethylphenol; 2,6-dioctadecyl-4-methylphenol; 2.4.6-tricyclohexylphenol; 2,6-di-t-butyl-4-methoxymethylphenol; linear or branched alkyl chain nonylphenols such as, for example, 2,6-di-nonyl-4-methylphenol; 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 their mixtures.

1.2 Alkylthiomethylphenols such as, for example: 2,4-dioctylthiomethyl-6-t-butylphenol; 2,4-dioctylthiomethyl-6-methylphenol; 2,4-dioctylthiomethyl-6-ethylphenol; 2,6-didodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkylated hydroquinones such as, for example: 2,6-di-t-butyl-4-methoxyphenol; 2,5-di-tbutylhydroquinone; 2,5-di-t-amylhydroquinone; 2,6-diphenyl-4-octadecyloxyphenol; 2,6-di-t-butylhydroquinone; 2,5-di-t-butyl-4-hydroxyanisole; 3,5-di-t-butyl-4-hydroxyanisole; 3,5-di-t-butyl-4-hydroxyphenyl stearate; bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate.

1.4 Tocopherols such as, for example: α-tocopherol, βtocopherol, y-tocopherol, δ-tocopherol and their mixtures (Vitamin E).

1.5 Hydroxylated thiodiphenyl ethers such as, for example: 2,2 '-thiobis- (6-t-butyl-4-methylphenol); 2,2'-thiobis- (4-octylphenol); 4,4'-thiobis- (6-t-butyl-3-methylphenol); 4,4'-thiobis- (6-t-butyl-2-methylphenol); 4,4 '-thiobis- (3,6-di-s-amylphenol); 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6 Alkylidene-bisphenols such as, for example: 2,2'-methylenebis- (6-t-butyl-4-methylenol); 2,2'-methylenebis- (6-t-butyl-4-ethylphenol); 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol]; 2,2'-methylenebis (4-methyl-6-cyclohexylphenol); 2,2'-methylenebis (6-nonyl-4-methylphenol); 2,2'-methylenebis (4,6-di-t-butylphenol); 2,2'-ethylidenebis (4,6-di-t-butylphenol); 2,2 '-ethylidenebis (6-t-butyl-4-isobutylphenol); 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol]; 2,2'-methylenebis [6- (a, α-dimethylbenzyl) -4-nonylphenol]; 4,4'-methylenebis (2,6-di-t-butylphenol); 4,4'-methylenebis (6-t-butyl-2-methylphenol); 1,1-bis- (5-t-butyl-4-hydroxy-2-methylphenyl) butane; 2,6-bis (3-t-butyl-5-methyl - 2-hydroxybenzyl) -4-methylenol; 1,1,3-tris- (5-t-butyl - 4-hydroxy-2-methylphenyl) butane; 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-ndodecylmercaptobutane; ethylene glycol bis [3,3-bis- (3'-t-butyl-4 '-hydroxyphenyl) butyrate]; bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene; bis- [2- (3'-t-butyl-2'-hydroxy-5'-methylbenzyl) - 6 - t-butyl-4-methylphenyl] terephthalate; 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane; 2,2-bis (3,5-di-t-butyl - 4 - hydroxyphenyl) propane; 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane; 1,1,5,5-tetra (5-t-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7 Benzyl compounds containing 0, N or S such as, for example: 3,5,3 ', 5'-tetra-t-butyl-4,4'-dihydroxybenzylether; octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate; tridecyl-4-hydroxy-3,5-di-t-butylbenzyl mercaptoacetate; tris (3,5-di-t-butyl-4-hydroxybenzyl) amine; bis {4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate; bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide; isooctyl-3,5-di-t-butyl-4-hydroxybenzyl mercaptoacetate.

1.8 Hydroxybenzylated malonates such as, for example: dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) malonate; dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) malonate; didodecylmercaptoethyl-2,2-bis (3,5 - di - t-butyl-4-hydroxybenzyl) malonate; bis [4- (1,1,3,3-tetramethylbutyl) phenyl] - 2,2 - bis (3,5-di-tbutyl-4-hydroxybenzyl) malonate.

1.9 Aromatic hydroxybenzyl compounds such as, for example: 1,3,5-tris (3,5-di - t-butyl - 4 - hydroxybenzyl) -2,4,6-trimethylbenzene; 1,4 - bis - (3,5-di-t-butylhydroxybenzyl) -2,3,5,6-tetramethylbenzene; 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) phenol.

1.10 Triazine compounds such as, for example: 2,4-bis (octylmercapto) -6- (3,5-di-t-butyl-4-hydroxyan - flax) -1,3,5-triazine; 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine; 2-octylmercapto-4,6-bis (3,5-di-t-butyl-4-hydroxyphenos-si) -1,3,5-triazine; 2,4,6-tris- (3,5-di-t-butyl— 4-hydroxyphenoxy) -1,2,3-triazine; 1,3,5-tris (3,5-dit-butyl-4-hydroxybenzyl) isocyanurate; 1,3,5-tris (4-t-butyl-3-hydroxy - 2, 6 - dimethylbenzyl) isocyanurate; 2,4,6-tris- (3,5-di-t-butyl-4-hydroxyphenylethyl) -1, -3,5-triazine; 1 / 3,5-tris (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine; 1,3,5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11 Benzylphosphonates such as, for example: dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphonate; diethyl-3,5-dit-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5-di-t-butyl-4-hydroxybenzyl phosphonate; dioctadecyl-5t-butyl-4-hydroxy-3-methylbenzylphosphonate; calcium salts of the monoethyl ester of 3,5-di-tbutyl-4-hydroxybenzylphosphonic acid.

1.12 Acylaminophenols such as, for example: 4-hydroxyl uranilide; 4-hydroxystearanilide; octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

1.13 Esters of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6 -hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris {hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxalamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospho - 2,6,7 - trioxabicyclo - [2.2.2] octane.

1.14 Esters of β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6 -hexanediol, 1,9-nonandiol, ethylene glycol, 1,2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν '-bis- (hydroxyethyl) oxalaramide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospho - 2,6,7 - trioxabicyclo - [2.2.2] octane.

1.15 Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexandiol, 1 , 9-nonandiol, ethylene glycol, 1,2-propandiol, neopentyl glycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxalamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospho - 2,6,7 - trioxabicyclo - [2.2.2] octane.

1.16 Esters of 3,5-di-t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, octanol, octadecanol, 1,6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propandiol, neopentyl glycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalamide, 3-thioundecanol, 3- thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl - 1 - phospho-2,6,7-trioxabicyclo [2.2.2] -octane.

1.17_ Amides of β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid such as, for example: Ν, Ν'-bis (3,5-di-t-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide; Ν, Ν'-bis (3,5-di-t-butyl - 4 - hydroxyphenylpropionyl) trimethylenediamide; N, N '-bis (3,5 - di-t-butyl-4-hydroxyphenylpropionyl) hydrazide; Ν, Ν'-bis [2- (3- [3,5-di-t-butyl-4-hydroxyphenyl] propion1 - oxy) ethyl] oxamide (Naugard <®> XL-1 by Uniroyal).

1.18 Ascorbic acid (vitamin C).

1.19 Amine antioxidants such as, for example, Ν, Ν'-di-isopropyl-p-phenylenediamine; N, -di-s-butyl-pphenylenediamine; N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine; N, N'-bis (1-ethyl-3-methylpentyl) -pphenylenediamine; N, N'-bis (1-methylheptyl) -p-phenylenediamine; N, N'-dicyclohexyl-p-phenylenediamine; Ν, Ν'-diphenyl-p-phenylenediamine; N, N'-bis (2-naphthyl) -p-phenylenediamine; N-isopropyl-N'-phenyl-pphenylenediamine; N- (1,3-dimethylbutyl) -N'-phenyl-pphenylenediamine; N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine; N-cyclohexyl-N'-phenyl-p-phenylenediamine; 4- (p-tolueneesulfonamido) diphenyleneamine; Ν, Ν'— di-methyl— N, Ν '- di-s-butyl-p-phenylenediamine; diphenylamine; N-allyldiphenylamine; 4-isopropoxyphenylamine; N-phenyl-1-naphthylamine; N- (4-t-octylphenyl) -1-naphthylamine; N-phenyl-2-naphthylamine; octylated diphenylamine such as, for example, p, p'-dit-octyldiphenylamine; 4-n-butylaminophenol; 4-butyrylaminophenol; 4-nonanoylaminophenol; 4-dodecanoylaminophenol; 4-octadecanoylaminophenol; bis- {4-methoxyphenyl) amine; 2,6-di-t-butyl-4-dimethylaminomethylphenol; 2,4'-diaminodiphenylmethane; 4,4'-diaminodiphenylmethane; N, Ν, Ν ', N'-tetramethyl-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; T-octylated N-phenyl-1-naphthylamine; mixture of mono- and dialkylated t-butyl / t-octyldiphenylamines; mixture of mono- and dialkylated nonyldiphenylamines; mixture of mono- and dialkylated dodecyldiphenylamines; mixture of mono- and dialkylated isopropyl / isoesyldiphenylamines; mixture of mono- and dialkylated t-butyl-di-phenylamines; 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine; phenothiazine; mixture of mono- and dialkylated tbutyl / t-octylphenothiazines; mixture of mono- and dialkylated t-octyl phenothiazines; N-allyl-phenothiazine; N, N, N ', N'-tetrafenes1-1,4-diaminobut-2-ene; N, N-bis {2, 2, 6, 6-tetramethyl-piperid-4-yl-hexamethylenediamine; bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate; 2, 2, 6, 6-tetramethylpiperidin-4-one; 2, 2, 6, 6-tetramethylpiperidin-4-ol.

2. Ultraviolet and light stabilizers.

2.1 Derivatives of 2- (2'-hydroxyphenyl) benzotriazoles such as, for example: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole; 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -benzotriazole; 2- (5'-t-bufi1-2'-hydroxyphenyl) benzotriazole; 2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- (3 ', 5'— di-t-butyl - 2' - hydroxyphenyl) -5-chlorobenzotriazole; 2- (3'-t-butyl-2'-hydroxy-5 '-methylphenyl) -5-chlorobenzotriazole; 2- (3'-sec-butyl-5'-t-butyl-2'-hydroxyphenyl) benzotriazole; 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazo-lo; 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole; 2- [3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl] benzotriazole; 2- [3 '- t - butyl - 2' - hydroxy-5 '- {2-octyloxycarbonyl ethyl) phenyl) -5-chloro-benzotria - zole; 2- [3'-t-butyl-5 '- (2- (2-ethylhexiloxy) carbons1-ethyl) -2' -hydroxyphenyl] -5-chlorobenzotriazole; 2- [3'-t-butyl - 2 hydroxy - 5 '- (2-methoxycarbonylethyl) phenyl] -5-chlorobenzotriazole; 2- [3'-t-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl] benzotriazole; 2- [3'-t-butyl-2'-hydroxy - 5 '- (2-octyloxycarbonylethyl) phenyl] benzotriazole; 2- [3'-t-butyl-5 '- (2- (2-ethylhexyloxy) carbonylethyl) - 2' - hydroxyphenyl) benzotriazole; 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) -benzotriazole; 2- [3'-t-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl] benzotriazole; 2,2'-methylenebis- [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; transesterification product of 2- [3'-t-butyl-5 '- (2-methoxycarbonyl-ethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300;

[R-CH2CH2-COO-CH2CH2-] 2- wherein R = 3 '- t - butyl-4'-hydroxy-5' -2H-benzotriazol-2-yl-phenyl; 2- \ 2'-hydroxy-3'- (a, α-dimethylbenzyl) - 5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2'-hydroxy-3 '- (1,1, -3,3-tetramethylbutyl) -5' - (a, α-dimethylbenzyl) phenyl] - benzotriazole.

2.2 Derivatives of 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4.2 ', 4'-trihydroxy-; 2'-hydroxy-4,4'-dimethoxy.

2.3 Esters of benzoic acids, optionally substituted, such as, for example: phenyl salicylate, 4-tbutylphenyl salicylate, octylphenyl salicylate, benzene resorcinol, bis (4-t-butylbenzoyl) resorcinol, dibenzoyl resorcinol, 2,4-di-t-butylphenyl -3,5-dit-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4 - hydroxybenzoate, octadecyl - 3,5 - di - t - butyl-4-hydroxybenzoate, 2-methyl - 4,6 - di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

2.4 Acrylates such as, for example, ethyl or iso-octyl αcian-β, β-diphenylacrylate; methyl α-carbomethoxycinnamate, methyl or butyl α-cyano-p-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N- (p-carbomethoxy-p-cyanovinyl) -2-methylindoline.

2.5 Nickel compounds such as, for example, nicomplexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], for example 1: 1 or 1: 2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-t-butylbenzyl-phosphonic, such as methyl or ethyl esters, complexes of nickel with kethoxime such as 2-hydroxy-4-methylphenyl undecyl kethoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

2.6 Sterically hindered amines and their N-alkoxy derivatives such as, for example: poly-methylpropyl-3-oxi- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane, polymethylpropyl-3-oxi- [4- (1,2,6,6-pentamethyl) piperidinyl] siloxane, bis- (2,2,6,6-tetramethyl-4 - piperidinyl) sebacate, bis- (2,2,6,6-tetramethyl -4-piperidinyl) succinate; bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; bis (1-octyloxy-2,2,6,6 - tetramethyl-4-piperidinyl) sebacate; bis (1,2,2,6,6-pentamethyl-4-piperidyl) -n-butyl-3,5-di-t-butyl-4-hydroxybenzyl-malonate; condensation product between 1- {2-hydroxyethyl) -2,2,6,6-te-between-4-hydroxypiperidine and succinic acid; condensation product, linear or cyclic, between N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-t-octylaminino-2,6-dichloro-1,3, 5-s-triazine; tris- (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate; tetrakis (2,2,6,6-tetramethyl-4-piperidyl) - 1,2,3,4 - butanotetracarboxylate; 1,1 '- (1,2 - ethanodiyl) bis- (3,3,5,5-tetramethylpiperazinone; 4-benzoyl-2,2,6,6-te-tramethylpiperidine; 4-stearyloxy-2,2 , 6,6-tetramethylpiperidine; bis (1,2,2,6,6 - pentamethylpipers - dil) -2-n-butyl-2- (2-hydroxy-3,5-di-t-butylbenzyl) - -malonate; 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro- [4.5] decan-2,4-dione; bis (1 - octyloxy— 2,2,6 , 6-tetramethylpiperidyl) sebacate; bis- (1-octyloxy-2,2,6, 6-tetramethylpiperidyl) succinate; condensation product, linear or cyclic, between N, N'-bis (2,2,6,6 -tetramethyl-4-piperidyl) hexamethyl-nediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; condensation product between 2-chloro-4,6-di- (4-n -butylaminino - 2,2,6,6 - tetramethylpiperidyl) -1,3,5-triazine and 1'1,2-bis (3-aminopropylamino) ethane; condensation product between 2-chloro-4,6 -di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane; 8-acetyl-3 -dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione; 3-dodecyl-1- (2,2,6,6-tetrametes 1-4-piperidyl) pyrrolidine-2,5-dione; 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione; mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; condensation product between Ι'Ν, Ν'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; condensation product between 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine, as well as 4-butylamino-2,2,6,6- tetramethylpiperidine (CAS Reg. No. [136504-96-6]; N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide; N- (1,2,2,6,6- pentamethyls 1-4-piperidii) -n-dodecylsuccinimide; 2-undecyl-7,7,9,9-tetramethyl-1-bone-3,8-diaza-4-oxospiro [4,5] decane; reaction product between 7,7,9,9-tetramethyl-2-cycloundecill-bones-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin; 1,1-bis (1,2,2,6, 6-pentamethyl-4-piperidyloxycarbonyl) - 2-- (4-methoxyphenyl) ethene; N, N'-bis - formyl-Ν, Ν'-bis (2,2,6,6-tetramethyl-4-piperidyl ) hexamethylenediamine; diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine; reaction product of the maleic anhydride / α-olefin copolymer with 2,2,6,6-tetramethyl -4-aminopiperidine or with 1,1,2,2,6-pentamethyl-4-aminopiperidine.

2.7 Oxaldiamides such as, for example: 4,4'-di-octyloxyoxanilide; 2,2'-diethoxyoxanilide; 2,2'-dioctyloxy-5,5 '-di-t-butoxanilide; 2,2'-didodecyloxy-5,5'-di-t-butyloxanilide; 2-ethoxy-2'-ethyloxanilide; N, N'-bis (3-dimethylaminopropyl) oxalamide; 2-ethoxy-5-t-butyl-2'-ethyloxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4'-di-t-butoxanilide; and mixtures of disubstituted ortho- and para-methoxy oxanilides and mixtures of disubstituted ortho- and para-ethoxy oxanilides.

2.8 2- (2-hydroxyphenyl) -1,3,5-triazines such as, 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-methylenyl) - 1,3,5-triazine; 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dime - tylphenyl) -1,3,5-triazine; 2- [2-hydroxy-4- (2-hydroxy - 3-butoxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine; 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -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- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -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-hexyloxyphenyl) -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-1-oxy) -2-hydroxypropyloxy] phenyl} -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3. "Metal-deactivators" such as, for example: N, N-diphenyloxalamide, N-salicylal-N'-salicyloyl-hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 -dit-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladipoyl dihydrazide, N'-diacetyladipoyl dihydrazide -bis (salicyloyl) oxallyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites such as, for example: triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) , diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di- t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis [2,4, fitris (t-butylphenyl)] pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis- (2,4-di-t-butylphenyl) -4,4 '- diphenylenediphosphonite, 6-isoott1-oxo-2,4,8,10-tetra-t-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10 -tetra-t-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocin, bis- (2,4-di-t-butyl-6-methylphenyl) methylphosphite, bis (2,4 -di-t-butyl-6-methylphenyl) ethylphosphite; 2,2 ', 2' '- nitrile [triethyl-tris (3,3', 5,5 '' - tetra-t-butyl - = - 1,1 '- biphenyl-2,2'-diyl) phosphite ]; 2-ethylhexyl- (3,3 ', 5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

5. Hydroxylamines such as, for example: N, N-dibenzylhydroxylamine; N, N-diethylhydroxylamine; N, N-dioctylhydroxylamine; N, N-di laurylhydroxylamine; N, N-dithetradecylhydroxylamine, N, N-hexadecylhydroxylamine; N, N-dioctadecylhydroxylamine; N-hexadecyl-N-octadecyl hydroxylamine; N-heptadecyl-N-octadecyl hydroxylamine; N, N-dialkylhydroxylamines derived from hydrogenated tallow amines.

6. Nitrons such as, for example: N-benzyl-α-f enylnitrone; N-ethyl-α-methyl-nitrone; N-octyl-α-heptylnitrone; N-lauryl-α-undecyl-nitrone; N-tetradecylα-tridecyl-nitrone; N-hexadecyl-α-pentadecyl-nitrone; N-octadecyl-α-heptadecyl-nitrone; N-hexadecyl-αheptadecyl-nitrone; N-octadecyl-α-pentadecyl-nitrone; N-heptadecyl-α-heptadecyl-nitrone; N-octadecyl-α-hexadecyl-nitrone; nitrones derived from hydrogenated tallow amines.

7. Thiosinerqists such as, for example: dilauryl thiodipropionate; distearyl thiodipropionate.

8. Agents that are capable of destroying peroxides such as, for example, esters of βthiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or 2-mercaptobenzimidazole zinc salt, zinc dibutyldithiocarbamate (β-dioctol tetra di methysulfide -dodecìlmercapto) propionate.

9. Stabilizers of polyamide such as, for example, copper salts in combination with iodine and / or phosphorus compounds, salts of divalent manganese.

10. Basic co-stabilizers such as, for example: melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of fatty acids with high molecular weight such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimony-pyrocatecolate, tin-pyrocatecolate, zinc-pyracatecolate.

11. Nucleating agents such as, for example: inorganic substances such as talc, metal oxides (for example, titanium dioxide or magnesium oxide), phosphates, carbonates or sulphates (preferably of alkaline earth metals}; organic compounds such as mono- or polycarboxyls and their salts (for example, 4-t-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, sodium benzoate); polymeric compounds such as ionic copolymers ("ionomers").

12. Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black , graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives such as, for example: plasticizers, pigments, lubricants, emulsifiers, rheological additives, catalysts, sliding agents, optical brighteners, anti-inflammatory agents (for example, brominated, chlorinated, phosphorated and mixed phosphorus / halogens), antistatic agents, expansion agents.

11. Benzofuranones and indolinones such as, for example: 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-t-butyl-benzofuran-2-one; 5,7-di-t-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one; 3,3'-bis [5,7-di-tbutyl - 3-- [4- (2-hydroxyethoxy) phenyl] benzofuran - 2 - one]; 5,7-di-t-butyl-3- (4-ethoxyphenyl) benzofuran-2-one; 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-t-butyl-benzofuran-2-one; 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-t-butyl-benzofuran-2-one; or those described in US Patent Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052 and 5,252,643; in German patents DE 4,316,611, 4,316,622 and 4,316,876; or in European patent applications No.

589.839 and 591.102.

In order to better understand the present invention and to put it into practice, some illustrative but not limitative examples of the present invention are given below.

EXAMPLE 1

Preparation of the compound having formula (la)

5 g (18 mmoles) of the compound having formula (III):

are reacted in toluene (5 ml) with methyldietoxysilane (4.1 ml; 3.4 g; 25 mmoles), in the presence of traces of hexachloroplatinic acid dissolved in isopropanol (10 μΐ of 2% solution by weight of H2PtCl6 ■ 6H2O) operating at 80 ° C for 4 hours.

The product thus obtained is subjected to fractional distillation at reduced pressure (1 torr) to give 5.9 g (yield 73% with respect to the compound having the starting formula (III)) of a colorless oil which distils at a boiler temperature of 240 ° C (1 torr) corresponding to the compound having formula (la).

EXAMPLE 2

Preparation of the polysiloxane having formula (II).

2.75 g (6.1 mmoles) of the compound having formula (la) obtained as described in Example 1, are dissolved in ethyl ether (15 ml) and are hydrolyzed by addition and contact of about 5 g of ice.

Two phases are obtained which, after dissolution of the ice, are stirred for 2 hours at room temperature. The ether phase is separated, washed with aqueous sodium bicarbonate and water and dried under vacuum.

The product obtained is added with 18 mg of dibutyl tin laurate and heated at 150 ° C, under reduced pressure, for eight hours.

An amber-yellow resinous compound is obtained corresponding to the polysiloxane having formula (II) in which n, p and q are equal to 0, consisting of a mixture of linear oligomers in which R1 = OH and R2 = H, and cyclic in which R1 and R2 represent a direct bond, having a number average molecular weight, measured by molecular exclusion chromatography [G.P.C .; eluent: tetrahydrofuran; detector: "triple detector" (refractive index; "light scattering"; differential viscometer)] equal to 6160.

EXAMPLE 3

Evaluation of the In n-heptane extralability of the compound object of the present Invention In HDPE platelets.

Commercial high density polyethylene (HDPE) "masterbatches" containing 10% by weight of stabilizing compound containing the following compounds are prepared:

(A): compound having formula:

obtained as described in European patents EP 162.523 and 182.415, consisting of a mixture of linear and cyclic oligomers, having a number average molecular weight, measured by molecular exclusion chromatography [G.P.C .; eluent: tetrahydrofuran; detector: "triple detector" (refractive index; "light scattering"; differential viscometer)] equal to 920;

(B): compound obtained as described above in Example 2;

(C): tetrakismethylene {3,5-di-t-butyl-4-hydroxyhydrocinnamate) methane (Anox 20 from Great Lakes);

(D): ethylene glycol bis [3,3-bis (3-t-butyl-4-hydroxyphenyl) butyrate] (Hostanox 03 by Hoechst).

The stabilizing compound is dissolved in toluene. High density polyethylene in powder form is added to the solution obtained and the solvent is subsequently removed by evaporation, under reduced pressure, under stirring.

The "masterbatches" thus obtained are mixed with other high density polyethylene in powder form so as to obtain mixtures containing 0.1% by weight of stabilizing compound.

Each of the aforementioned "masterbatches" is extruded in a Brabender-type laboratory die with a screw speed of 50 rpm and a temperature profile from the head to the tail zone varying from 180 ° C to 240 ° C. The extruded samples are cut into granules and pressed for 3 minutes at 260 ° C, obtaining plates having a thickness of 1 mm. Using the aforesaid platelets, the amount of stabilizing compound remaining after extraction with n-heptane is evaluated by infrared spectrophotometry (IR) (said extraction is carried out using a Soxhlet type extractor). For this purpose, the relative variation of the IR absorbance at 1735 cm <'1> is calculated with respect to a platelet not added and the percentage of antioxidant compound left is expressed as:

RE = (A0 - A) / A0 x 100

in which:

RE = resistance to extraction;

A0 = absorbance value before the extraction treatment;

A = absorbance value after the extraction treatment.

The results obtained are reported in Table 1 and in Figure 1.

TABLE 1

EXAMPLE 4

Evaluation of the extractability in "wildcard petroleum" of the compounds object of the present invention in HDPE platelets.

Platelets obtained as described above in Example 3, are subjected to extraction by immersion in "petroleum jelly", under stirring, at 80 ° C.

The results obtained are reported in Table 2 and Figure 2.

TABLE 2

Claims (18)

CLAIMS 1. Stabilizing compounds containing a sterically hindered phenolic group and a hydrolyzable silica function having general formula (I): in which: R and R ', the same or different from each other, represent a halogen atom as chlorine; a linear or branched C1-C4 acyloxy group; a linear or branched C1-C4 alkyloxy group; as well as stabilizing compounds, consisting of the complex resinous structures derived from the hydrolysis and condensation of the aforementioned stabilizing compounds having general formula (I), having general formula (II) I) in which : R1 represents a hydroxyl group; R2 represents a hydrogen atom; or, R1 and R2 jointly represent a direct link giving rise to cyclic structures; m is an integer between 1 and 2000 extremes included; n, p and q, each independently, are an integer between 0 and 50 inclusive; R3 represents a hydrogen atom; or one of the following groups having general formula (IIa), (IIb), (IIe) or (IId): in which p ', q' and η ', each independently, are an integer between 1 and 50 inclusive; m and R3 have the same meanings described above. 2. Stabilizing compounds according to claim 1, wherein the stabilizing compounds having general formula (II) have an average molecular weight comprised between 396 and 756000. 3. Stabilizing compounds according to claim 2, wherein the stabilizing compounds having general formula (II) have an average molecular weight comprised between 1000 and 30000. 4. Stabilizing compounds according to claim 3, wherein the stabilizing compounds having general formula (II) have an average molecular weight comprised between 1500 and 15000. 5. Process for the preparation of the stabilizing compounds having general formula (I) according to any one of the preceding claims, comprising the silylation reaction of a spherically hindered phenol having formula (III): with a silylating agent having general formula (IV): in which R and R 'have the same meanings described above. 6. Process according to claim 5, wherein the silylation reaction is carried out at a temperature ranging from 0 ° C to 200 ° C, using quantities of reagents ranging from stoichiometric ones to an excess of the silylation agent. 7. Process according to claim 5 or 6, wherein the silylation reaction is catalyzed by metal catalysts, ultraviolet radiation and radical initiators. 8. Process according to any one of claims 5 to 7, wherein the silylation reaction is carried out in an inert organic solvent, selected from aliphatic, cycloaliphatic or aromatic hydrocarbons, or esters. 9. Process according to any one of claims 5 to 8, in which the times of the aforesaid silylation reaction are comprised between 0.5 hours and 10 hours. 10. Process for the preparation of the stabilizing compounds having general formula (II) according to any one of claims 1 to 4, comprising the hydrolysis to the silyl functionality of the stabilizing compounds having general formula (I) according to claim 1, for contact with water or with ambient humidity, at room temperature (20 ° C-25 ° C) or at a temperature above or below the ambient one and subsequent condensation between the silanol groups deriving from the aforementioned hydrolysis. 11. Process according to claim 10, wherein the condensation between the silanol groups is catalyzed by acidic or basic agents, by soaps or by metal esters as well as by organo-metal compounds. 12. Process according to claim 11, wherein the condensation reaction is carried out at room temperature (20 ° C-25 ° C), as well as at temperatures lower or higher than said ambient temperature. 13. Process for the preparation of the stabilizing compounds having general formula (II) according to any one of claims 1 to 4, according to which the hydrolysis of the silicic functionality and a partial condensation of the product are carried out externally to the organic polymer to stabilize hydrolysis thus obtained which is subsequently introduced into the organic polymer to be stabilized within which the completion of the condensation takes place, obtaining the complex resinous structures having general formula (II). 14. Polymeric compositions containing an organic polymer and an effective amount of one or more stabilizing compounds having general formula (I) or (II) according to any one of the preceding claims. 15. Polymeric compositions according to claim 14, wherein the stabilizing compounds having general formula (I) or (II) are used in combination with other conventional additives. 16. Polymeric compositions according to claim 14 or 15, wherein the organic polymer is selected from cross-linked polyolefins and polyolefins obtained by catalytic polymerization in which the catalytic system is metallocene or "single site catalyst". 17. Use of the polymeric compositions according to any one of claims 14 to 16, as insulating material for electric wires, cables, pipes. 18. Products obtained from the processing of the polymeric compositions according to any one of claims 14 to 16.