ITMI992204A1

ITMI992204A1 - STABILIZED POLYMERIC COMPOSITIONS AND THEIR USE IN ELECTRIC WIRES AND CABLES

Info

Publication number: ITMI992204A1
Application number: IT1999MI002204A
Authority: IT
Inventors: Luciano Pallini; Carlo Neri; Rossella Farris; Marco Bizzarri
Original assignee: Great Lakes Chemical Europ
Priority date: 1999-10-21
Filing date: 1999-10-21
Publication date: 2001-04-21
Also published as: ITMI992204A0; IT1315250B1

Description

"COMPOSIZIONI POLIMERICHE STABILIZZATE E LORO UTILIZZO IN FILI ELETTRICI E CAVI" "STABILIZED POLYMER COMPOSITIONS AND THEIR USE IN ELECTRICAL WIRES AND CABLES"

DESCRIZIONE DESCRIPTION

La presente invenzione riguarda composizioni polimeriche stabilizzate. The present invention relates to stabilized polymeric compositions.

Più in particolare la presente invenzione riguarda composizioni polimeriche stabilizzate comprendenti una poliolefina ed almeno un composto antiossidante di tipo tio-fenolico ed il loro utilizzo in fili elettrici e cavi. More particularly, the present invention relates to stabilized polymeric compositions comprising a polyolefin and at least one antioxidant compound of the thio-phenolic type and their use in electric wires and cables.

La presente invenzione riguarda inoltre i fili elettrici ed i cavi rivestiti dalle suddette composizioni polimeriche. The present invention also relates to electric wires and cables coated by the aforementioned polymeric compositions.

Nel brevetto USA 3,773,812 sono descritti polisilicati derivati dalla condensazione di 4,4'-bisfenoli particolarmente utili nella stabilizzazione di poliolefine che possono essere utilizzate per la produzione di films, parti di automobili, ecc. Non viene citato il possibile uso di dette poliolefine in fili elettrici e cavi. In US patent 3,773,812 polysilicates derived from the condensation of 4,4'-bisphenols are described, particularly useful in the stabilization of polyolefins which can be used for the production of films, car parts, etc. The possible use of said polyolefins in electric wires and cables is not mentioned.

Nel brevetto USA 4,238,505 viene descritto un metodo per reticol are pol imeri quali, ad esempio le poliolefine, e stabilizzarli contro la degradazione causata dall'ossigeno e/o dal calore. Viene inoltre citata la crescente importanza nell'uso delle poliolefine reticolate quale materiale isolante per fili elettrici e cavi. Nel suddetto brevetto viene detto che il composto antiossidante utilizzato deve avere almeno un gruppo sililalchenilico nella molecola. In US patent 4,238,505 a method is described for crosslinking polymers such as, for example, polyolefins, and stabilizing them against degradation caused by oxygen and / or heat. The growing importance of the use of cross-linked polyolefins as an insulating material for electrical wires and cables is also mentioned. In the above patent it is stated that the antioxidant compound used must have at least one silylalkenyl group in the molecule.

I problemi che si incontrano nella stabilizzazione dei polimeri organici derivano essenzialmente da fenomeni di incompatibilità tra il composto antiossidante ed il polimero e da fenomeni di rilascio del composto antiossidante da parte del polimero stesso. Nel caso particolare di polimeri utilizzati per il rivestimento di fili elettrici e cavi, inoltre, molto spesso le guaine polimeriche sono immerse in una paraffina ("petroleum jelly") che ha il compito, tra gli altri, di isolare ulteriormente il filo di rame dall'ambiente esterno. Poiché, usualmente, l'antiossidante impiegato per la stabilizzazione del polimero ha una buona affinità per il "petroleum jelly" si verifica, nel tempo, una progressiva riduzione della concentrazione dell'antiossidante presente nel polimero a causa della estrazione effettuata da detto "petroleum jelly". 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 the particular case of polymers used for the coating of electric wires and cables, moreover, very often the polymeric sheaths are immersed in a paraffin ("petroleum jelly") which has the task, among others, of further isolating the copper wire from external environment. Since, usually, the antioxidant used for the stabilization of the polymer has a good affinity for the "petroleum jelly", a progressive reduction of the concentration of the antioxidant present in the polymer occurs over time due to the extraction carried out by said "petroleum jelly" ".

La Richiedente ha ora sorprendentemente trovato che, contrariamente a quanto descritto nell'arte nota, specifici silil-derivati di 4,4'-tio-bisfenoli non aventi gruppi sililachenilici nella molecola, sono particolarmente efficaci nella stabilizzazione di poliolefine utili in fili elettrici e cavi (ad esempio, cavi telefonici). The Applicant has now surprisingly found that, contrary to what is described in the known art, specific silyl derivatives of 4,4'-thio-bisphenols not having silylachenyl groups in the molecule, are particularly effective in the stabilization of polyolefins useful in electric wires and cables. (for example, telephone cables).

Costituiscono pertanto oggetto della presente invenzione composizioni polimeriche stabilizzate comprendenti: Therefore, the subject of the present invention are stabilized polymeric compositions comprising:

una poliolefina; ed a polyolefin; and

almeno un composto antiossidante di tipo tiofenolico avente formula generale (I): at least one antioxidant compound of the thiophenol type having general formula (I):

in cui: in which:

n rappresenta un numero intero compreso tra 1 e 100 estremi inclusi; n represents an integer between 1 and 100 inclusive;

R rappresenta un atomo di idrogeno; oppure un gruppo avente formula generale (II): R represents a hydrogen atom; or a group having general formula (II):

in cui R1 rappresenta un gruppo alchilico C1-C3 lineare o ramificato; wherein R1 represents a linear or branched C1-C3 alkyl group;

Z rappresenta un gruppo OH; oppure un gruppo avente formula (III): Z represents an OH group; or a group having formula (III):

oppure, R e Z rappresentano congiuntamente un legame diretto dando luogo a strutture cicliche; or, R and Z jointly represent a direct bond giving rise to cyclic structures;

Y rappresenta un gruppo avente formula generale (IV): Y represents a group having general formula (IV):

in cui R1 rappresenta un gruppo alchilico C1-C3 lineare o ramificato. wherein R1 represents a linear or branched C1-C3 alkyl group.

Poliolefine utili allo scopo della presente invenzione sono scelte tra le resine termoplastiche. Polyolefins useful for the purpose of the present invention are selected from the thermoplastic resins.

Dette resine possono essere omopolimeri o copolimeri ottenuti da due o più comonomeri, oppure miscele di due o più di detti polimeri, usualmente utilizzati in forma di film, fogli, tubi, così come rivestimenti e/o materiali isolanti per fili elettrici e cavi. Said resins can be homopolymers or copolymers obtained from two or more comonomers, or mixtures of two or more of said polymers, usually used in the form of films, sheets, pipes, as well as coatings and / or insulating materials for electric wires and cables.

Monomeri utili nella produzione dei suddetti omopolimeri e copolimeri possono avere da 2 a 20 atomi di carbonio, preferibilmente da 2 a 12 atomi di carbonio. Esempi di detti monomeri sono le αolefine quali, ad esempio, etilene, propilene, 1-butene, 1-esene, 4-metil-1-pentene, 1-ottene; esteri insaturi quali, ad esempio, vinil acetato, etil acrilato, metil acrilato, metil metacrilato, tbutil acrilato, n-butil acrilato, n-butil metacrilato, 2-etilesil acrilato, ed altri alchil acrilati; diolefine quali, ad esempio, 1,4-pentadiene, 1,3-esadiene, 1,5-esadiene, 1,4-ottadiene ed etilene-norbornene che è, usualmente, il terzo monomero nei terpolimeri; altri monomeri quali, ad esempio, stirene, p-metil stirene, α-metil stirene, p-cloro stirene, vinil naftalene, ed aril-olefine simili; nitrili quali, ad esempio, acrilonitrile, metacrilonitrile, α-cloroacrilonitrile; vinil metil chetone, vinil metil etere, vinilidene cloruro, anidride maleica, vinil cloruro, vinil alcool, tetrafluoroetilene, clorotrifluoroetilene; acido acrilico, acido metacrilico, ed altri acidi insaturi simili. Monomers useful in the production of the above homopolymers and copolymers can have from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms. Examples of said monomers are αolefins such as, for example, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene; unsaturated esters such as, for example, vinyl acetate, ethyl acrylate, methyl acrylate, methyl methacrylate, tbutyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, and other alkyl acrylates; diolefins such as, for example, 1,4-pentadiene, 1,3-hexadiene, 1,5-hexadiene, 1,4-octadiene and ethylene-norbornene which is usually the third monomer in terpolymers; other monomers such as, for example, styrene, p-methyl styrene, α-methyl styrene, p-chloro styrene, vinyl naphthalene, and similar aryl-olefins; nitriles such as, for example, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; vinyl methyl ketone, vinyl methyl ether, vinylidene chloride, maleic anhydride, vinyl chloride, vinyl alcohol, tetrafluoroethylene, chlorotrifluoroethylene; acrylic acid, methacrylic acid, and other similar unsaturated acids.

Gli omopolimeri ed i copolimeri sopra riportati, possono essere non-alogenatì, oppure possono essere alogenati in modo convenzionale, generalmente con cloro e bromo. Esempi di polimeri alogenati sono polivinil cloruro, polivinilidene cloruro, politetrafluoroetilene . The homopolymers and copolymers reported above can be non-halogenated, or they can be halogenated in a conventional way, generally with chlorine and bromine. Examples of halogenated polymers are polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene.

Preferiti allo scopo della presente invenzione sono gli omopolimeri ed i copolimeri dell'etilene e del propilene, sia in forma non-alogenata che in forma alogenata. Inclusi nei preferiti sono anche i terpolimeri quali, ad esempio, le gomme a base del monomero etilene/propilene/diene. Preferred for the purpose of the present invention are the homopolymers and copolymers of ethylene and propylene, both in the non-halogenated and in the halogenated form. Also included in the favorites are terpolymers such as, for example, rubbers based on the ethylene / propylene / diene monomer.

Altri esempi di polimeri a base di etilene sono i seguenti: omopolimero dell'etilene ad elevata pressione; copolimero dell'etilene e di una o più α-olefine aventi da 3 a 12 atomi di carbonio; omopolimero o copolimero dell'etilene avente una funzione silano idrolizzabile graffata alla loro struttura; copolimero dell'etilene e di un alchenil trialcossi silano quale, ad esempio, il trimetossi vinil silano; oppure un copolimero di una α-olefina avente da 2 a 12 atomi di carbonio e di un estere insaturo avente da 4 a 20 atomi di carbonio quale, ad esempio, il copolimero etilene/etil acrilato o vinil acetato; terpolimero etilene/etil acrilato o vinil acetato/silano idrolizzabile; copolimeri etilene/etil acrilato o vinil acetato aventi una funzione silano idrolizzabile graffata alla loro struttura. Other examples of ethylene-based polymers are the following: homopolymer of ethylene at high pressure; copolymer of ethylene and one or more α-olefins having from 3 to 12 carbon atoms; homopolymer or copolymer of ethylene having a hydrolyzable silane function grafted to their structure; copolymer of ethylene and an alkenyl trialkoxy silane such as, for example, trimethoxy vinyl silane; or a copolymer of an α-olefin having from 2 to 12 carbon atoms and an unsaturated ester having from 4 to 20 carbon atoms such as, for example, the ethylene / ethyl acrylate or vinyl acetate copolymer; ethylene / ethyl acrylate or vinyl acetate / hydrolysable silane terpolymer; ethylene / ethyl acrylate or vinyl acetate copolymers having a hydrolyzable silane function grafted to their structure.

Per quanto riguarda il polipropilene, utili allo scopo della presente invenzione sono: omopolimeri e copolimeri del propilene e di una o più αolefine. Allo scopo della presente invenzione possono essere utilizzati omopolimeri e copolimeri del propilene e di una o più α-olefine in cui la parte di copolimero basata sul polipropilene è almeno il 60% in peso sul peso totale del copolimero. As regards polypropylene, useful for the purpose of the present invention are: homopolymers and copolymers of propylene and of one or more αolefins. For the purpose of the present invention, homopolymers and copolymers of propylene and of one or more α-olefins can be used in which the part of the copolymer based on the polypropylene is at least 60% by weight of the total weight of the copolymer.

Il polipropilene può essere preparato attraverso procedimenti convenzionali, ad esempio, il procedimento descritto nel brevetto USA 4,414,132. Polipropilene preferito è quello a base di comonomeri α-olefinici aventi da 2 a 12 atomi di carbonio. The polypropylene can be prepared through conventional processes, for example, the process described in US patent 4,414,132. Preferred polypropylene is that based on α-olefinic comonomers having from 2 to 12 carbon atoms.

Particolarmente utilizzati per il rivestimento di fili elettrici o cavi sono le resine termoplastiche reticolate. Gli omopolimeri od i copolimeri possono essere reticolati con perossidi organici, oppure per renderli idrolizzabili, possono essere graffati con un alchenil trialcossi silano in presenza di un perossido organico che agisce come generatore di radicali liberi o come catalizzatore. Alchenil trialcossi silani utili allo scopo sono scelti tra i vinil trialcossi silani quali, ad esempio, vinil trimetossi silano, vinil trietossisilano, vinil triisopropossi silano. I radicali alchenilici ed alcossilicipossono avere da 1 a 30 atomi di carbonio, preferibilmente da 1 a,12. I polimeri idrolizzabili possono essere reticolati in ambiente umido in presenza di un catalizzatore per la condensazione di gruppi silanoli quale, ad esempio, dibutil stagno dilaurato, diottil stagno maleato, acetato stannoso, ottoato stannoso, naftenato di piombo, ottoato di zinco, ferro 2-etil esoato, ed altri carbossilati metallici. Particularly used for the coating of electric wires or cables are cross-linked thermoplastic resins. The homopolymers or copolymers can be crosslinked with organic peroxides, or to make them hydrolyzable, they can be grafted with an alkenyl trialkoxy silane in the presence of an organic peroxide which acts as a generator of free radicals or as a catalyst. Alkenyl trialkoxy silanes useful for this purpose are selected from vinyl trialkoxy silanes such as, for example, vinyl trimethoxy silane, vinyl triethoxysilane, vinyl triisopropoxy silane. Alkenyl and alkoxy radicals can have from 1 to 30 carbon atoms, preferably from 1 to 12. The hydrolysable polymers can be cross-linked in a humid environment in the presence of a catalyst for the condensation of silanol groups such as, for example, dibutyl tin dilaurate, dioctyl tin maleate, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, iron 2- ethyl hexoate, and other metal carboxylates.

Gli omopolimeri od i copolimeri dell'etilene in cui l'etilene è il comonomero principale e gli omopolimeri ed i copolimeri del propilene in cui il propilene è il comonomero principale possono essere di seguito indicati come polietilene e polipropilene rispettivamente. The homopolymers or copolymers of ethylene in which ethylene is the main comonomer and the homopolymers and copolymers of propylene in which propylene is the main comonomer can be referred to below as polyethylene and polypropylene respectively.

I composti antiossidanti aventi formula generale (I) utili allo scopo della presente invenzione possono essere preparati attraverso vari procedimenti . The antioxidant compounds having general formula (I) useful for the purpose of the present invention can be prepared by various processes.

Un procedimento per la preparazione dei composti antiossidanti aventi formula generale (I) comprende la reazione del 4,4'-tio-bis(3-metil-6-tbutil-fenolo) (noto con il nome commerciale di Lowinox TBM-6 della Great Lakes) avente formula (V): A process for the preparation of the antioxidant compounds having general formula (I) comprises the reaction of 4,4'-thio-bis (3-methyl-6-tbutyl-phenol) (known under the commercial name of Lowinox TBM-6 from Great Lakes) having formula (V):

con un dialchil-dicloro-silano avente formula generale (VI): with a dialkyl-dichloro-silane having general formula (VI):

in cui R1 ha gli stessi significati sopra descritti, in presenza di un solvente organico inerte, a temperatura compresa tra -10°C e 150°C, preferibilmente tra 20°C e 120°C, per un tempo compreso tra 2 ore e 48 ore, preferibilmente tra 10 ore e 20 ore. in which R1 has the same meanings described above, in the presence of an inert organic solvent, at a temperature between -10 ° C and 150 ° C, preferably between 20 ° C and 120 ° C, for a time between 2 hours and 48 hours, preferably between 10 hours and 20 hours.

Solventi organici inerti utili allo scopo del suddetto procedimento sono scelti tra i solventi idrocarburici quali, ad esempio, toluene, eptano, cicloesano, ecc. Inert organic solvents useful for the purpose of the above process are selected from hydrocarbon solvents such as, for example, toluene, heptane, cyclohexane, etc.

Durante la suddetta reazione si sviluppa acido cloridrico, come prodotto di reazione, che viene rimosso per mezzo di una base o mediante ebollizione del solvente. Basi utili allo scopo sono, ad esempio, piridina, trietilammina, ecc. During the above reaction hydrochloric acid develops as a reaction product, which is removed by means of a base or by boiling the solvent. Useful bases for this purpose are, for example, pyridine, triethylamine, etc.

I composti aventi formula generale (I) ottenuti al termine della suddetta reazione sono miscele di composti il cui peso molecolare medio dipende dal rapporto molare in cui sono miscelati il 4,4'-tiobis (3-metil-6-t-butil-fenolo) avente formula (V) ed il dialchil-dicloro-silano avente formula generale (VI) e dal grado di completezza della reazione. Allo scopo, il 4,4'-tio-bis(3-metil-6-t-butil-fenolo) avente formula (V) ed il dialchil-diclorosilano avente formula generale (VI) vengono miscelati in rappporto molari da 3:1 a 1:3, preferibilmente da 2:1 a 1:2. The compounds having general formula (I) obtained at the end of the above reaction are mixtures of compounds whose average molecular weight depends on the molar ratio in which 4,4'-thiobis (3-methyl-6-t-butyl-phenol ) having formula (V) and dialkyl-dichloro-silane having general formula (VI) and the degree of completeness of the reaction. For this purpose, 4,4'-thio-bis (3-methyl-6-t-butyl-phenol) having formula (V) and dialkyl-dichlorosilane having general formula (VI) are mixed in molar ratios of 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

I composti antiossidanti aventi formula generale (I) vengono utilizzati in quantità compresa tra 0,01% e 5% sul peso totale del polimero da stabilizzare, preferibilmente tra 0,05% e 3%, ancora più preferibilmente tra 0,1% ed 1%. The antioxidant compounds having general formula (I) are used in quantities ranging from 0.01% to 5% of the total weight of the polymer to be stabilized, preferably between 0.05% and 3%, even more preferably between 0.1% and 1 %.

Detti composti antiossidanti possono essere utilizzati tal quali oppure in combinazione con altri additivi convenzionali. Detti additivi vengono aggiunti in quantità compresa tra circa 0,01% e circa 5% in peso sul peso delle composizioni polimeriche da stabilizzare, preferibilmente tra circa 0.1% e circa 3% in peso. A titolo di esempio vengono sotto riportati alcuni tra gli additivi utilizzati. Said antioxidant compounds can be used as such or in combination with other conventional additives. Said additives are added in quantities ranging from about 0.01% to about 5% by weight of the weight of the polymeric compositions to be stabilized, preferably between about 0.1% and about 3% by weight. By way of example, some of the additives used are listed below.

1. Antiossidanti 1. Antioxidants

1. 1 Monofenoli alchilati come, ad esempio : 2, 6-dit-butil-4-metilfenolo; 2-t-butil-4 , 6-dimetilf enolo; 2. 6-di-t-butil-4-etilfenolo; 2, 6-di-t-butil-4-n-butilfenolo; 2 , 6-di-t-butil-4-isobutilfenolo; 2, 6-diciclopentil-4-metilfenolo; 2- (α-metilcicloesil) -4. 6-dimetilfenolo; 2, 6-diottadecil-4-metilf enolo; 2.4.6-tricicloesilfenolo; 2,6-di-t-butil-4-metossimetilfenolo; nonilfenoli a catena alchilica lineare o ramificata quali, ad esempio, 2,6-di-nonil-4-metilfenolo; 2,4-dimetil-6-{1'-metilundec-1'-il)fenolo; 2,4-dimetil-6-(1'-metileptadec-1'-il)fenolo; 2,4-dimetil-6- (1'-metiltridec-1'-il)fenolo; e loro miscele . 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 Alchiltiometilfenoli come, ad esempio: 2,4-diottiltiometil-6-t-butilfenolo; 2,4-diottiltiometil-6-metilfenolo; 2,4-diottiltiometil-6-etilfenolo; 2,6-didodeciltiometil-4-nonilfenolo. 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 Idrochinoni ed idrochinoni alchilati come, ad esempio: 2,6-di-t-butil-4-metossifenolo; 2,5-di-tbutilidrochinone; 2,5-di-t-amilidrochinone; 2,6-difenil-4-ottadecilossifenolo; 2,6-di-t-butilidrochinone; 2,5-di-t-butil-4-idrossianisolo; 3,5-di-t-butil-4-idrossianisolo; 3,5-di-t-butil-4-idrossifenil stearato; bis (3,5-di-t-butil-4-idrossifenil)adipato. 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 Tocoferoli come, ad esempio: α-tocoferolo, βtocoferolo, γ-tocoferolo, δ-tocoferolo e loro miscele (Vitamina E). 1.4 Tocopherols such as, for example: α-tocopherol, βtocopherol, γ-tocopherol, δ-tocopherol and their mixtures (Vitamin E).

1.5 Eteri tiodifenilici idrossilati come, ad esempio: 2 ,2'-tiobis-(6-t-butil-4-metilfenolo); 2,2'-tiobis- (4-ottilfenolo); 4,4'-tiobis-(6-t-butil-3-metilfenolo) ; 4,4'-tiobis-{6-t-butil-2-metilfenolo); 4,4 '-tiobis-(3,6-di-s-amilfenolo); 4,4'-bis-(2,6-dimetil-4-idrossifenil)disolfuro. 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 Alchiliden-bisfenoli come, ad esempio: 2,2'-metilenebis- (6-t-butil-4-metilfenolo); 2,2'-metilenebis- (6-t-butil-4-etilfenolo); 2,2'-metilenebis[4-metil-6- (α-metilcicloesil)fenolo]; 2,2'-metilenebis (4-metil-6-cicloesilfenolo); 2,2'-metilenebis(6-nonil-4-metilienolo) ; 2,2'-metilenebis(4,6-di-t-butilfenolo ); 2,2’-etilidenebis(4,6-di-t-butilfenolo) ; 2,2'-etilidenebis(6-t-butil-4-isobutilfenolo) ; 2,2'-metilenebis[6-(α-metilbenzil)-4-nonilfenolo]; 2,2'-metilenebis[6-(a,α-dimetilbenzil)-4-nonilfenolo]; 4,4'-metilenebis(2,6-di-t-butilfenolo); 4,4'-metilenebis (6-t-butil-2-metilfenolo); 1,1-bis-(5-t-butil-4-idrossi-2-metilfenil)butano; 2,6-bis-(3-t-butil-5-metil--2-idrossibenzil)-4-metilfenolo; 1,1,3-tris- (5-t-butil— 4-idrossi-2-metilfenil)butano; 1,1-bis (5-t-butil-4-idrossi-2-metilfenil)-3-ndodecilmercaptobutano; etilenglicole bis[3,3-bis-{3'-t-butil-4 '-idrossifenil)butirrato]; bis(3-t-butil-4-idrossi-5-metilfenil)diciclopentadiene; bis-[2-(3'-t-butil-2 '-idrossi-5'-metilbenzil)— 6--t-butil-4-metiltenil]tereftalato; 1,1-bis(3,5-dimetil-2-idrossifenil)butano; 2,2-bis(3,5-di-t-butil— 4— idrossifenil)propano; 2,2-bis(5-t-butil-4-idrossi-2-metilfenil)-4-n-dodecilmercaptobutano; 1,1,5,5-tetra (5-t-butil-4-idrossi-2-metilfenil)pentano. 1.6 Alkylidene-bisphenols such as, for example: 2,2'-methylenebis- (6-t-butyl-4-methylphenol); 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-methylenol); 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-methylphenol; 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-methyltenyl] 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 Composti benzilici contenenti 0, N o S come, ad esempio : 3,5,3',5'-tetra-t-butil-4,4'-diidrossidibenziletere; ottadecil-4-idrossi-3,5-dimetilbenzilmercaptoacetato; tridecil-4-idrossi-3,5-di-t-butilbenzilmercaptoacetato ; tris(3,5-di-t-butil-4-idrossibenzil)ammina; bis(4-t-butil-3-idrossi-2,6-dimetilbenzil)ditiotereftalato; bis(3,5-di-t-butil-4-idrossibenzil)solfuro; isoottil-3,5-di-t-butil-4-idrossibenzilmercaptoacetato . 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 Maionati idrossibenzilati come, ad esempio: diottadecil-2,2-bis (3,5-di-t-butil-2-idrossibenzil)-maionato; diottadecil-2- (3-t-butil-4-idrossi-5-metilbenzil)maionato; didodecilmercaptoetil-2,2-bis-(3,5--di— t-butil-4-idrossibenzil)maionato; bis[4-(1,1,3,3-tetrametilbutil)fenil]--2,2— bis(3,5-di-tbutil-4-idrossibenzil)maionato . 1.8 Hydroxybenzylated maionates such as, for example: dioctadecyl-2,2-bis (3,5-di-t-butyl-2-hydroxybenzyl) -maionate; dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) maionate; didodecylmercaptoethyl-2,2-bis- (3,5-di-t-butyl-4-hydroxybenzyl) maionate; bis [4- (1,1,3,3-tetramethylbutyl) phenyl] - 2,2— bis (3,5-di-tbutyl-4-hydroxybenzyl) maionate.

1.9 Composti idrossibenzilici aromatici come, ad esempio: 1,3,5-tris(3,5-di— t-butil— 4— idrossibenzil)-2,4,6-trimetilbenzene; 1,4--bis— (3,5-di-t-butilidrossibenzil)-2,3,5, 6-tetrametilbenzene; 2,4,6-tris (3,5-di-t-butil-4-idrossibenzil)fenolo. 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 Composti triazinici come, ad esempio: 2,4-bis (ottilmercapto)-6-(3,5-di-t-butil-4-idrossiani-~ lino)-1,3,5-triazina; 2-ottilmercapto-4,6-bìs(3,5-di-t-butil-4-idrossianilino) -1,3,5-triazina; 2-ottilmercapto-4 ,6-bis(3,5-di-t-butil-4-idrossifenos--si)-1,3,5-triazina; 2,4,6-tris-(3,5-di-t-butil--4--idrossifenossi)-1,2, 3-triazina; 1,3,5-tris(3,5-dit-butil-4-idrossibenzil) isocianurato; 1,3,5-tris(4-t-butil-3-idrossi--2 ,6--dimetilbenzil)isocianurato; 2,4, 6-tris-(3,5-di-t-butil-4-idrossifeniletil)-1,-3 ,5-triazina; 1,3,5-tris(3,5-di-t-butil-4-idrossifenilpropionil) esaidro-1,3,5-triazina; 1,3,5-tris-(3,5-dicicloesil-4-idrossibenzil)isocianurato. 1.10 Triazine compounds such as, for example: 2,4-bis (octylmercapto) -6- (3,5-di-t-butyl-4-hydroxian- ~ 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 Benzilfosfonati come, ad esempio: dimetil-2,5-di-t-butil-4-idrossibenzilfosfonato; dietil-3,5-dit-butil-4-idrossibenzilfosfonato; diottadecil-3, 5-di-t-butil-4-idrossibenzilfosfonato; diottadecil-5-t-butil-4-idrossi-3-metilbenzilfosfonato; sali di calcio dell'estere monoetilico dell'acido 3,5-di-tbutil-4-idrossibenzilfosfonico. 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-hydroxybenzylphosphonate; dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate; calcium salts of the monoethyl ester of 3,5-di-tbutyl-4-hydroxybenzylphosphonic acid.

1.12 Acilamminofenoli come, ad esempio: 4-idrossilauranilide; 4-idrossistearanilide ; ottil-N-(3,5-di-t-butil-4-idrossifenil)carbammato . 1.12 Acylaminophenols such as, for example: 4-hydroxyl uranilide; 4-hydroxystearanilide; octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

1.13 Esteri dell'acido β-(3,5-di-t-butil-4-idrossifenil)propionico con alcooli monoidrici o poliidrici come, ad esempio: metanolo, etanolo, n-ottanolo, i-ottanolo, ottadecanolo, 1,6-esandiolo, 1,9-nonandiolo, glicole etilenico, 1,2-propandiolo, glicole neopentilico, glicole tiodietilenico, glicole dietilenico, glicole trietilenico, pentaeritritolo, tris(idrossietil) isocianurato, N,N'-bis-(idrossietil)ossalammide, 3-tioundecanolo, 3-tiopentadecanolo, trimetilesandiolo, trimetilolpropano, 4-idrossimetil-1-fosfo— 2,6,7--triossabiciclo--[2.2.2]ottano. 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 Esteri dell'acido β-(5-t-butil-4-idrossi-3-metilfenil )propionico con alcooli monoidrici o poliidrici come, ad esempio: metanolo, etanolo, n-ottanolo, i-ottanolo, ottadecanolo, 1,6-esandiolo, 1,9-nonandiolo, glicole etilenico, 1,2-propandiolo, glicole neopentilico, glicole tiodietilenico, glicole dietilenico, glicole trietilenico, pentaeritritolo, tris(idrossietil) isocianurato, Ν,Ν'-bis-(idrossietil)ossalammide, 3-tioundecanolo, 3-tiopentadecanolo, trimetilesandiolo, trimetilolpropano, 4-idrossimetil-1-fosfo--2,6,7--triossabiciclo--[2.2.2]ottano. 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) oxalamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospho - 2,6,7 - trioxabicyclo - [2.2.2] octane.

1.15 Esteri dell'acido β-(3,5-dicicloesil-4-idrossifenil)propionico con alcooli monoidrici o poliidrici come, ad esempio: metanolo, etanolo, n-ottanolo, i-ottanolo, ottadecanolo, 1,6-esandiolo, 1,9-nonandiolo, glicole etilenico, 1,2-propandiolo, glicole neopentilico, glicole tiodietilenico, glicole dietilenico, glicole trietilenico, pentaeritritolo, tris(idrossietil) isocianurato, N,N'-bis-(idrossietil)ossalammide, 3-tioundecanolo, 3-tiopentadecanolo, trimetilesandiolo, trimetilolpropano, 4-idrossimetil-1-fosfo— 2,6,7— triossabiciclo— [2.2.2]ottano . 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 Esteri dell'acido 3,5-di-t-butil-4-idrossifenil)acetico con alcooli monoidrici o poliidrici come, ad esempio: metanolo, etanolo, n-ottanolo, iottanolo, ottadecanolo, 1,6-esandiolo, 1,9-nonandiolo, glicole etilenico, 1,2-propandiolo, glicole neopentilico, glicole tiodietilenico, glicole dietilenico, glicole trietilenico, pentaeritritolo, tris (idrossietil) isocianurato, N,N'-bis(idrossietil)ossalammide, 3-tioundecanolo, 3-tiopentadecanolo, trimetilesandiolo, trimetilolpropano, 4-idrossimetil— 1— fosfo-2,6,7-triossabiciclo[2.2.2]-ottano. 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_ Ammidi dell’acido β-(3,5-di-t-butil-4-idrossifenil)propionico come, ad esempio: Ν,Ν'-bis (3,5-di-t-butil-4-idrossifenilpropionil)esametilenediammide; N,N '-bis{3,5-di-t-butil--4— idrossifenilpropionil)trimetilenediammide; N,N'-bis(3,5--di-t-butil-4-idrossifenilpropionil)idrazide; Ν,Ν'-bis [2-(3-[3,5-di-t-butil-4-idrossifenil]propionil--ossi)etil]ossammide (Naugard<® >XL-1 della Uniroyal). 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; N, N '-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] propionyl - oxy) ethyl] oxamide (Naugard <®> XL-1 by Uniroyal).

1.18 Acido ascorbico (vitamina C). 1.18 Ascorbic acid (vitamin C).

1.19 Antiossidanti amminici come, ad esempio, Ν,Ν'-di-isopropil-p-fenilenediammina; Ν,Ν'-di-s-butil-pfenilenediammina; Ν,Ν'-bis(1,4-dimetilpentil)-p-fenilenediammina; Ν,Ν'-bis(1-etil-3-metilpentil)-pfenilenediammina; Ν,Ν'-bis(1-metileptil)-p-fenilenediammina; Ν,Ν'-dicicloesil-p-fenilenediammina; N,N'-difenil-p-fenilenediammina; Ν,Ν'-bis(2-naftil)-p-fenilenediammina ; N-isopropil-N'-fenil-pfenilenediammina; N-(1,3-dimetilbutil)-N'-fenil-pfenilenediammina; N-(1-metileptil)-N'-fenil-p-fenilenediammina; N-cicloesil-N' -fenil-p-fenilenediammina; 4-(p-toluenesulfonammido)difenileneammina; N,N'—di-metil— N,N'--di-s-butil-p-fenilenediammina; difenilammina; N-allildifenilammina; 4-isopropossidifenilammina; N-fenil-1-naftilammina; N-(4-t-ottilfenil)-1-naftilammina ; N-fenil-2-naf tilammina; difenilammina ottilata quale, ad esempio, p,p'-dit-ottildifenilammina ; 4-n-butilamminofenolo; 4-butirrilamminofenolo; 4-nonanoilamminofenolo; 4-dodecanoilamminofenolo; 4-ottadecanoilamminofenolo; bis- (4-metossifenil)ammina; 2,6-di-t-butil-4-dimetilamminometilfenolo; 2,4'-diamminodifenilmetano; 4,4'-diamminodifenilmetano; N,N,N',N'-tetrametil-4,4'-diamminodifenilmetano; 1,2-bis[(2-metilfenil)-ammino]etano; 1,2-bis(fenilammino)propano; (o-tolil)biguanide; bis[4-(1',3'-dimetilbutil)fenil]-ammina; N-fenil-1-naftilammina t-ottilata; miscela di t-butil/t-ottildifenilammine mono- e dialchilate; miscela di nonildifenilammine mono- e dialchilate; miscela di dodecildifenilammine mono- e dialchilate; miscela di isopropil/isoesildifenilammine mono- e dialchilate; miscela di t-butil-di-fenilammine mono- e dialchilate; 2,3-diidro-3,3-dimetil-4H-1,4-benzotiazina; fenotiazina; miscela di tbutil/t-ottilfenotiazine mono- e dialchilate; miscela di t-ottil-fenotiazine mono- e dialchilate; N-allil-fenotiazina; Ν,Ν,Ν',Ν'-tetrafenil-1,4-diamminobut-2-ene; N,N-bis(2,2,6,6-tetrametil-piperid-4-il-esametilenediammina; bis(2,2,6,6-tetrametilpiperidin-4-il)sebacato; 2,2,6,6-tetrametilpiperidin-4-one; 2,2,6,6-tetrametilpiperidin-4-olo. 1.19 Amine antioxidants such as, for example, Ν, Ν'-di-isopropyl-p-phenylenediamine; Ν, Ν'-di-s-butyl-pphenylenediamine; Ν, Ν'-bis (1,4-dimethylpentyl) -p-phenylenediamine; Ν, Ν'-bis (1-ethyl-3-methylpentyl) -pphenylenediamine; Ν, Ν'-bis (1-methylheptyl) -p-phenylenediamine; Ν, Ν'-dicyclohexyl-p-phenylenediamine; N, N'-diphenyl-p-phenylenediamine; Ν, Ν'-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; N, N'-di-methyl - N, N '- 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, N, N ', 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; Ν, Ν, Ν ', Ν'-tetraphenyl-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. Stabilizzanti ai raggi ultravioletti ed alla luce. 2. Ultraviolet and light stabilizers.

2.1 Derivati di 2-(2'-idrossifenil)benzotriazoli come, ad esempio: 2-(2'-idrossi-5'-metilfenil)benzotriazolo ; 2-(3',5'-di-t-butil-2'-idrossifenil)-benzotriazolo; 2-(5'-t-butil-2'-idrossifenil)benzotriazolo; 2-[2'-idrossi-5'-{1,1,3,3-tetrametilbutil)fenil]benzotriazolo; 2-(3',5'— di-t-butil— 2'— idrossifenil)-5-clorobenzotriazolo; 2-(3'-t-butil-2 '-idrossi-5'-metilfenil)-5-clorobenzotriazolo; 2-(3'-sec-butil-5'-t-butil-2'-idrossifenil)benzotriazolo; 2-(2'-idrossi-4'-ottilossifenil)benzotriazo— lo; 2-(3',5'-di-t-amil-2'-idrossifenil)benzotriazolo; 2-[3',5'-bis (a,α-dimetilbenzil)-2'-idrossifenil]benzotriazolo; 2-[3'--t— butil--2'— idrossi-5'-(2-ottilossicarboniletil)fenil)-5-cloro-benzotria--zolo; 2-[3'-t-butil-5'-(2-(2-etilesilossi)carboni1-etil) -2'-idrossifenil]-5-clorobenzotriazolo; 2-[3 ' -t-butil--2 idrossi--5'— (2-metossicarboniletil)fenil]-5-clorobenzotriazolo; 2-[3'-t-butil-2'-idrossi-5 '-(2-metossicarboniletil)fenil]benzotriazolo; 2-[3'-t-butil-2 '-idrossi--5'--(2-ottilossicarboniletil)fenil]benzotriazolo; 2- [3'-t-butil-5'-(2-(2-etilesilossi)carboniletil)--2 '— idrossifenil)benzotriazolo; 2- (3'-dodecil-2'-idrossi-5'-metilfenil)-benzotriazolo; 2- [3'-t-butil-2'-idrossi-5'-(2-isoottilossicarboniletil)fenil]benzotriazolo; 2,2'-metilenebis- [4-(1,1,3,3-tetrametilbutil)-6-benzotriazol-2-il-fenolo]; prodotto di transesterificazione del 2- [3’-t-butil-5’-{2-metossicarbonil-etil)-2' -idrossifenil]-2H-benzotriazolo con il polietilene glicole 300; 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-butyl-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) benzotriazoal; 2- (3 ', 5'-di-t-amyl-2'-hydroxyphenyl) benzotriazole; 2- [3 ', 5'-bis (a, α-dimethylbenzyl) -2'-hydroxyphenyl] benzotriazole; 2- [3 '- t— butyl - 2'— hydroxy-5' - (2-octyloxycarbonylethyl) 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- in cui R = 3'— t— butil-4'-idrossi-5'-2H-benzotriazol-2-il-fenil; 2- [2' -idrossi-3'- (a,α-dimetilbenzil)— 5'--(1,1,3,3-tetrametilbutil)fenil]benzotriazolo; 2- [2' -idrossi-3'-(1,1,-3,3-tetrametilbutil)-5'- (a,α-dimetilbenzil)fenil]— benzotriazolo. [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 Derivati di 2-idrossibenzofenoni come, ad esempio: 4-idrossi-; 4-metossi-; 4-ottilossi; 4-decilossi-; 4-dodecilossi-; 4-benzilossi-; 4,2',4'-triidrossi-; 2'-idrossi-4,4'-dimetossi. 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 Esteri di acidi benzoici, opzionalmente sostituiti, come, ad esempio: fenil salicilato, 4-tbutilfenil salicilato, ottilfenil salicilato, benzoli resorcinolo, bis{4-t-butilbenzoil)resorcinolo, dibenzoil resorcinolo, 2,4-di-t-butilfenil-3,5-dit-butil-4-idrossibenzoato, esadecil-3,5-di-t-butil-4— idrossibenzoato, ottadecil— 3,5— di--t— butil-4-idrossibenzoato, 2-metil— 4,6— di-t-butilfenil-3,5-di-t-butil-4-idrossibenzoato. 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 Acrilati come, ad esempio, etil od iso-ottil αciano-β,β-difenilacrilato; metil α-carbometossicinnamato, metil o butil α-ciano-β-metil-p-metossicinnamato, metil α-carbometossi-p-metossicinnamato, N- (β-carbometossi-β-cianovinil)-2-metilindolina. 2.4 Acrylates such as, for example, ethyl or iso-octyl αcian-β, β-diphenylacrylate; methyl α-carbomethoxycinnamate, methyl or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

2.5 Composti del nichel come, ad esempio, Nicomplessi del 2,2'-tio-bis-[4-(1,1,3,3-tetrametilbutil)fenolo], ad esempio complessi 1:1 o 1:2, con o senza leganti addizionali come n-butilammina, trietanolammina o N-cicloesildietanolammina, nichel dibutilditiocarbammato, sali di nichel di esteri monoalchilici dell'acido 4-idrossi-3,5-di-t-butilbenzil-fosfonico, come esteri metilici o etilici, complessi del nichel con chetossime come 2-idrossi-4-metilfenil undecil chetossima, complessi del nichel di l-fenil-4-lauroil-5-idrossipirazolo con o senza leganti addizionali. 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 Ammine stericamente impedite e loro N-alcossi derivati come, ad esempio: poli-metilpropil-3-ossi-[4-(2,2,6,6-tetrametil)piperidinil]silossano, polimetilpropil-3-ossi- [4-(1,2,2,6,6-pentametil)pìperidinil]silossano, bis- (2,2,6,6-tetrametil-4—piperidinil)sebacato; bis-(2,2,6,6-tetrametil-4-piperidinil)succinato; bis(1,-2,2,6,6-pentametil-4-piperidinil)sebacato; bis(1-ottilossi-2,2,6,6—tetrametil-4-piperidinil)sebacato; bis(1,2,2,6,6-pentametil-4-piperidil)-n-butil-3,5-di-t-butil-4-idrossibenzil — maionato; prodotto di condensazione tra la l-(2-idrossietil)-2,2,6,6-te-tra-4-idrossipiperidina e l'acido succinico; prodotto di condensazione, lineare o ciclico, tra la Ν,Ν'-bis(2,2,6,6-tetrametil-4-piperidil)esametilenediammina e la 4-t-ottilammino-2, 6-dicloro-1,3,5-s-triazina; tris-(2,2,6,6-tetrametil-4-piperidil)nitrilotriacetato; tetrakis (2,2,6,6-tetrametil-4-piperidil)— 1,2,3,4— butanotetracarbos silato; 1,1'--(1,2--etanodiil)bis-(3,3,5,5-tetrametilpiperazinone; 4-benzoil-2,2,6,6-te-trametilpiperidina ; 4-stearilossi-2,2,6,6-tetrametilpiperidina; bis(1,2,2,6,6— pentametilpiperi--dil)-2-n-butil-2- (2-idrossi-3,5-di-t-butilbenzil)--maionato; 3-n-ottil-7,7,9,9-tetrametil-1,3,8-triazaspiro- [4.5]decan-2,4-dione; bis(1--ottilossi— 2,2,6,6-tetrametilpiperidil) sebacato; bis-(1-ottilossi-2,2, 6,6-tetrametilpiperidil)succinato; prodotto di condensazione, lineare o ciclico, tra la N,N'-bis (2,2,6,6-tetrametil-4-piperidil)esametile— nediammina e la 4-morfolino-2,6-dicloro-1,3,5-triazina; prodotto di condensazione tra la 2-cloro-4,6-di- (4-n-butilammino— 2,2,6,6— tetrametilpiperidil)-1,3,5-triazina e l'1,2-bis(3-amminopropilammino)etano; prodotto di condensazione tra la 2-cloro-4,6-di- (4-n-butilammino-1,2,2,6,6-pentametilpiperidil)-1,3,5-triazina e l'1,2-bis(3-amminopropilammino)etano; 8-acetil-3-dodecil-7,7,9,9-tetrametil-1,3,8-triazaspiro [4.5]decano-2,4-dione; 3-dodecil-1- (2,2,6,6-tetrametil-4-piperidil)pirrolidin-2,5-dione; 3-dodecil-1-(1,2,2,6,6-pentametil-4-piperidil)pirrolidin-2,5-dione; miscela di 4-esadecilossi- e 4-stearilossi-2,2,6,6-tetrametilpiperidina; prodotto di condensazione tra Ι'Ν,Ν'-bis (2,2,6,6-tetrametil-4-piperidil)esametilenediammina e la 4-cicloesilammino-2,6-dicloro-1,3,5-triazina; prodotto di condensazione tra l'1,2-bis(3-amminopropilammino)etano e la 2,4,6-tricloro-1,3,5-triazina, così come la 4-butilammino-2,2,6,6-tetrametilpiperidina (CAS Reg. No. [136504-96-6]; N- (2,2,6,6-tetrametil-4-piperidil)-n-dodecilsuccinimmide; N-(1,2,2,6,6-pentametil-4-piperidil)-n-dodecilsuccinimmide; 2-undecil-7,7,9,9-tetrametil-1-ossa-3,8-diaza-4-ossospiro [4,5]decano; prodotto di reazione tra il 7,7,9,9-tetrametil-2-cicloundecill-ossa-3,8-diaza-4-ossospiro [4,5]decano e l'epicloridrina; 1,1-bis(1,2,2,6,6-pentametil-4-piperidilossicarboni1)--2-- (4-metossifenil)etene; N,N'-bis— formil-Ν,Ν'-bis (2,2,6,6-tetraraetil-4-piperidil)esametilenediammina; diestere dell'acido 4-metossimetilenemalonico con la 1,2,2,6,6-pentametil-4-idrossipiperidina; prodotto di reazione del copolimero anidride maleica/α-olefina con la 2,2,6,6-tetrametil-4-amminopiperidina o con la 1,1,2,2,6-pentametil-4-amminopiperidina . 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- (1,2,2,6,6-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-maionate; condensation product between 1- (2-hydroxyethyl) -2,2,6,6-te-between-4-hydroxypiperidine and succinic acid; condensation product, linear or cyclic, between Ν, Ν'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-t-octylamino-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 - butanotetracarbosilate; 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) - mayionate; 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 of 2-chloro-4,6-di- (4-n-butylamino - 2,2,6,6— tetramethylpiperidyl) -1,3,5-triazine and 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-tetramethyl -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- pentamethyl-4-piperidyl) -n-dodecylsuccinimide; 2-undecyl-7,7,9,9-tetramethyl-1-bone-3,8-diaza-4-oxospyr [4,5] decane; reaction product between 7,7,9,9-tetramethyl-2-cycloundecyl-bone-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin; 1,1-bis (1,2,2,6, 6-pentamethyl-4-piperidyloxycarbon1) - 2-- (4-methoxyphenyl) ethene; N, N'-bis— formyl-Ν, Ν'-bis (2,2,6,6-tetraraethyl-4-piperidyl) hexamethylenediamine; 4-methoxymethylenemalonic acid diester 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. 1 Ossaldiammidi come, ad esempio: 4,4'-di-ottilossiossanilide; 2,2'-dietossiossanilide; 2,2'-diottilossi-5,5 '-di-t-butossanilide; 2,2'-didodecilossi-5,5 '-di-t-butilossanilide; 2-etossi-2'-etilossanilide; N,N'-bis{3-dimetilamminopropil)ossalammide; 2-etossi-5-t-butil-2 '-etilossanilide e sue miscele con 2-etossi-2'-etil-5,4'-di-t-butossanilide; e miscele di orto- e para-metossi ossanilidi disostituite e miscele di orto- e para-etossi ossanilidi disostituite. 2. 1 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-idrossifenil)-1,3,5-triazine come, ad esempio: 2,4,6-tris(2-idrossi--4— ottilossifenil)-1,3,5-triazina; 2-(2-idrossi-4-ottilossifenil)-4,6-bis (2,4-dimetilfenil)— 1,3,5— triazina; 2-(2,4-diidrossifenil)-4,6-bis (2,4-dimetilfenil)-1,3,5-triazina; 2,4-bis-(2-idrossi-4-propilossifenil)-6-(2,4-dimetilfenil)-1,3,5-triazina; 2-(2-idrossi-4-ott.ilossifenil)--4,6--bis (4-metilfenil)— 1,3,5-triazina; 2-(2-idrossi-4-dodecilossifenil)-4,6-bis (2,4-dime— tilfenil)-1,3,5-triazina; 2-[2-idrossi-4-(2-idrossi--3— butilossipropilossi)fenil]-4,6-bis(2,4-dimetilfenil)-1,3,5-triazina; 2-[2-idrossi-4-(2-idrossi-3-ottilossi-propilossi)fenil]-4,6-bis (2,4-dime— tilfenil)-1,3,5-triazina; 2-(2-idrossi-4-tridecilossifenil)-4,6-bis- (2,4-dimetilfenil)-1,3,5-triazina; 2-[4-(dodecilossi/tridecilossi-2-idrossipropossi)-2-idrossifenil]-4,6-bis (2,4-dimetilfenil)-1,3,-5-triazina; 2- [2-idrossi-4-(2-idrossi-3-dodecilossipropossi)fenil]-4,6-bis (2,4-dimetilfenil)-1,3,5— triazina; 2- (2-idrossi-4-esilossifenil)-4,6-difenil-1,3,5-triazina; 2- (2-idrossi-4-metossifenil)-4,6-difenil-1,3,5-triazina; 2,4,6-tris[2-idrossi— 4-(3-butossi-2-idrossipropossi)fenil]-1,3,5-triazina; 2- (2-idrossifenil)-4-(4-metossifenil)-6-fenil-1,3,5-triazina; 2-{2-idrossi-4-[3-(2-etilesil-1-ossi)-2-idrossipropilossi]fenil}-4,6-bis (2,4-dimetilfenil)-1,3,5-triazina. 2.8 2- (2-hydroxyphenyl) -1,3,5-triazine 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-oct.yloxyphenyl) - 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- (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" come, ad esempio: N,N-difenilossalammide, N-salicilal-N'-saliciloil-idrazina, N,Ν'-bis{saliciloil)idrazina, Ν,Ν'-bis(3,5-dit-butil-4-idrossifenilpropionil)idrazina, 3-saliciloilammino-1,2,4-triazolo, bis(benzilidene)ossallil diidrazide, ossanilide, isoftaloil diidrazide, sebacoil bisfenilidrazide, N,N'-diacetiladipoil diidrazide, N,N '-bis(saliciloil)ossallil diidrazide, Ν,Ν'-bis (saliciloil)tiopropionil diidrazide. 3. "Metal-deactivators" such as, for example: N, N-diphenyloxalamide, N-salicylal-N'-salicyloyl-hydrazine, N, Ν'-bis {salicyloyl) hydrazine, Ν, Ν'-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, -bis (salicyloyl) oxalyl dihydrazide, Ν, Ν'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Fosfiti e fosfoniti come, ad esempio: trifenil fosfito, difenil alchil fosfiti, fenil dialchil fosfiti, tris(nonilfenil)fosfito, trilauril fosfito, triottadecil fosfito, distearil pentaeritritol difosfito, tris(2,4-di-t-butilfenil)fosfito, diisodecil pentaeritritol difosfito, bis(2,4-di-t-butilfenil)pentaeritritol difosfito, bis(2,6-di-t-butil-4-metilfenil)pentaeritritol difosfito, diisodecilossipentaeritritol difosfito, bis(2,4-di-t-butil-6-metilfenil)pentaeritritol difosfito, bis [2,4,fitris (t-butilfenil)]pentaeritritol difosfito, tristearil sorbitol trifosfito, tetrakis-(2,4-di-t-butilfenil)-4,4'-difenilenedifosfonito, 6-isoottilossi-2,4,8,10-tetra-t-butil-12H-dibenzo [d,g]-1,3,2-diossafosfocina, 6-fluoro-2,4,8,10-tetra-t-butil-12-metil-dibenzo [d,g]-1,3,2-diossafosfocina, bis-(2,4-di-t-butil-6-metilfenil)metilfosfito, bis(2,4-di-t-butil-6-metilfenil)etilfosfito; 2, 2' , 2' ' -nitrilo[trietil-tris (3,3',5,5''-tetra-t-butil--1,1'--bifenil-2,2'-dìil)fosfito]; 2-etilesil- (3,3',5,5'-tetra-t-butil-1,1'-bifenil-2,2'-diil)fosfito. 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-isooctyloxy-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. Idrossilammine come, ad esempio: N,N-dibenzilidrossilammina; N,N-dietilidrossilammina; N,N-diottilidrossilammina; N,N-dilaurilidrossilammina; N,N-ditetradecilidrossilammina, N,N-diesadecilidrossilammina; N,N-diottadecilidrossilammina; N-esadecil-N-ottadecilidrossilammina; N-eptadecil-N-ottadecilidrossilammina; N,N-dialchilidrossilammine derivate dalle ammine del sego idrogenate. 5. Hydroxylamines such as, for example: N, N-dibenzylhydroxylamine; N, N-diethylhydroxylamine; N, N-dioctylhydroxylamine; N, N-dilaurylhydroxylamine; 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. Nitroni come, ad esempio: N-benzil-α-f enilnitrone; N-etil-α-metil-nitrone ; N-ottil-α-eptilnitrone; N-lauril-α-undecil-nitrone; N-tetradecilα-tridecil-nitrone; N-esadecil-α-pentadecil-nitrone; N-ottadecil-α-eptadecil-nitrone; N-esadecil-αeptadecil-nitrone; N-ottadecil-α-pentadecil-nitrone; N-eptadecil-α-eptadecil-nitrone; N-ottadecil-αesadecil-nitrone ; nitroni derivati dalle ammine del sego idrogenate. 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. Tiosinergisti come, ad esempio: dilauril tiodipropionato; distearil tiodipropionato. 7. Thiosynergists such as, for example: dilauryl thiodipropionate; distearyl thiodipropionate.

8. Agenti che sono in grado di distruggere i perossidi come, ad esempio, esteri dell'acido βtiodipropionico come lauril, stearil, miristil o tridecil esteri, mercaptobenzimidazolo o sale di zinco del 2-mercaptobenzimidazolo, zinco dibutilditiocarbammato, diottadecildisolfuro, pentaeritritol tetrakis (β-dodecilmercapto)propionato. 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-dioctolodecyldisulfide -dodecilmercapto) propionate.

9. Stabilizzanti della poliammide come, ad esempio, sali di rame in combinazione con composti dello iodio e/o del fosforo, sali del manganese divalente. 9. Stabilizers of polyamide such as, for example, copper salts in combination with iodine and / or phosphorus compounds, salts of divalent manganese.

10. Co-stabilizzanti basici come, ad esempio: melammina, polivinilpirrolidone, dicianodiammide, triallil cianurato, derivati dell'urea, derivati dell'idrazina, animine, poliammidi, poliuretani, sali dei metalli alcalini e sali dei metalli alcalino-terrosi di acidi grassi ad elevato peso molecolare come, ad esempio, Ca-stearato, Zn-stearato, Mg-stearato, Mg-behenato, Na-ricinoleato, K-palmitato, antimonio-pirocatecolato, stagno-pirocatecolato, zinco-piracatecolato. 10. Basic co-stabilizers such as, for example: melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, animines, 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. Agenti nucleanti come, ad esempio: sostanze inorganiche quali talco, ossidi metallici (ad esempio, diossido di titanio od ossido di magnesio), fosfati, carbonati o solfati (preferibilmente di metalli alcalino-terrosi); composti organici quali acidi mono- o policarbossilici e loro sali (ad esempio, acido 4-t-butilbenzoico, acido adipico, acido difenilacetico, succinato di sodio, benzoato di sodio); composti polimerici quali copolimeri ionici ( "ionomers"). 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 polycarboxylic acids 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. Cariche ed agenti rinforzanti come, ad esempio: carbonato di calcio, silicati, fibre di vetro, perline di vetro ("glass beads"), amianto, talco, caolino, mica, solfato di bario, ossidi ed idrossidi metallici, nero fumo, grafite, farina di legno e farine o fibre di altri prodotti naturali, fibre sintetiche. 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. Altri additivi come, ad esempio: plastificanti, pigmenti, lubrificanti, emulsionanti, additivi reologici, catalizzatori, agenti di scivolamento, brillantanti ottici, agenti antifiammma (ad esempio, bromurati, clorurati, fosforati e misti fosforo/alogeni), agenti antistatici, agenti di espansione. 13. Other additives such as, for example: plasticizers, pigments, lubricants, emulsifiers, rheological additives, catalysts, sliding agents, optical brighteners, anti-inflammatory agents (e.g. brominated, chlorinated, phosphorated and mixed phosphorus / halogens), antistatic agents, expansion agents.

11. Benzofuranoni ed indolinoni come, ad esempio: 3-[4- (2-acetossietossi)fenil]-5,7-di-t-butil-benzofuran-2-one; 5,7-di-t-butil-3-[4-(2-stearoilossietossi)fenil]benzofuran-2-one; 3,3'-bis[5,7-di-tbutil— 3— [4-(2-idrossietossi)fenil]benzofuran--2— one]; 5,7-di-t-butil-3-(4-etossifenil)benzofuran-2-one; 3-(4-acetossi-3,5-dimetilfenil)-5,7-di-t-butil-benzofuran-2-one; 3-(3,5-dimetil-4-pivaloilossifenil)-5,7-di-t-butil-benzofuran-2-one; oppure quelli descritti nei brevetti USA No. 4,325,863, 4,338,244, 5,175,312, 5,216,052 e 5,252,643; nei brevetti tedeschi DE 4,316,611, 4,316,622 e 4,316,876; o nelle domande di brevetto europeo No. 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 e 591,102. 589.839 and 591.102.

Le composizioni polimeriche oggetto della presente invenzione possono essere utilizzate, quale materiale isolante, in fili elettrici e cavi (ad esempio, cavi telefonici). The polymeric compositions object of the present invention can be used, as insulating material, in electric wires and cables (for example, telephone cables).

Di conseguenza, sono ulteriore oggetto della presente invenzione i fili elettrici ed i cavi rivestiti da dette composizioni polimeriche. Consequently, electric wires and cables coated with said polymeric compositions are a further object of the present invention.

Allo scopo di meglio comprendere la presente invenzione e per mettere in pratica la stessa, vengono di seguito riportati alcuni esempi illustrativi ma non limitativi della presente invenzione. 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.

ESEMPIO 1 EXAMPLE 1

60 g (0,167 moli) di 4,4'-tio-bis(3-metil-6-tbutil-fenolo) (noto con il nome commerciale di Lowinox TBM6 della Great Lakes) e 33,9 g (0,335 moli) di trietilammina vengono disciolti, a temperatura ambiente, in 400 mi di toluolo. 60 g (0.167 mol) of 4,4'-thio-bis (3-methyl-6-tbutyl-phenol) (known as Great Lakes' Lowinox TBM6) and 33.9 g (0.335 mol) of triethylamine they are dissolved, at room temperature, in 400 ml of toluene.

A detta soluzione vengono aggiunti, lentamente per gocciolamento, 21,6 g (0,167 moli) di dimetildicloro-silano: la miscela ottenuta viene fatta reagire a temperatura ambiente per 12 ore. To said solution, 21.6 g (0.167 moles) of dimethyldichloro-silane are slowly added by dropping: the mixture obtained is reacted at room temperature for 12 hours.

Il cloridrato dell'ammina che si forma come prodotto di reazione viene filtrato e la fase organica ottenuta viene lavata per 3 volte con 200 mi di acqua. The amine hydrochloride which forms as reaction product is filtered and the organic phase obtained is washed 3 times with 200 ml of water.

Il solvente viene eliminato per evaporazione a pressione ridotta, operando ad una temperatura di 150°C e riducendo gradatamente la pressione fino a 1 mm/Hg. The solvent is eliminated by evaporation under reduced pressure, operating at a temperature of 150 ° C and gradually reducing the pressure up to 1 mm / Hg.

Si ottengono 62 g di un prodotto vetroso (avente temperatura di transizione vetrosa (Tg) pari a 93°C) di colore giallino avente la seguente formula: 62 g of a glassy product (having a glass transition temperature (Tg) equal to 93 ° C) of a yellowish color are obtained, having the following formula:

costituito da una miscela di oligomeri lineari e ciclici, avente peso molecolare medio numerico, misurato mediante cromatografia ad esclusione molecolare [G.P.C.; eluente: tetraidrofurano; rivelatore: "triple detector" (indice di rifrazione; "light scattering"; viscosimetro differenziale)] pari a 11500. 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 11500.

ESEMPIO 2 EXAMPLE 2

Valutazione della attività stabilizzante dei composti oggetto della presente invenzione in granuli di HDPE . Evaluation of the stabilizing activity of the compounds object of the present invention in HDPE granules.

Vengono preparati granuli di polietilene ad elevata densità (HDPE) commerciale allo 0,1% in peso di composto stabilizzante contenenti i seguenti composti : Commercial high density polyethylene (HDPE) granules are prepared at 0.1% by weight of stabilizing compound containing the following compounds:

(A): composto ottenuto come sopra descritto nell'Esempio 1; (A): compound obtained as described above in Example 1;

(B): 4,4'-tio-bis (3-metil-6-t-butil-fenolo) (noto con il nome commerciale di Lowinox TBM6 della Great Lakes). (B): 4,4'-thio-bis (3-methyl-6-t-butyl-phenol) (known under the trade name of Lowinox TBM6 from Great Lakes).

mediante estrusione in una trafila da laboratorio tipo Brabender con una velocità della coclea pari a 50 rpm ed un profilo di temperature dalla zona di testa alla zona di coda variabile dai 180°C ai 240°C. I campioni vengono ripetutamente estrusi e vengono valutati il "Melt Flow Index" (MFI) e l'indice di giallo (YI) dopo la 1-, la 3- e la 5-estrusione (come confronto vengono estrusi anche granuli di HDPE non stabilizzato). I risultati ottenuti vengono riportati in Tabella 1. by extrusion in a Brabender-type laboratory die with a screw speed of 50 rpm and a temperature profile from the head to the tail area ranging from 180 ° C to 240 ° C. The samples are repeatedly extruded and the "Melt Flow Index" (MFI) and the yellow index (YI) are evaluated after 1-, 3- and 5-extrusion (as a comparison, unstabilized HDPE granules are also extruded ). The results obtained are reported in Table 1.

TABELLA 1 TABLE 1

ESEMPIO 3 EXAMPLE 3

Valutazione della attività stabilizzante dei composti oggetto della presente invenzione in placchette di HDPE. Evaluation of the stabilizing activity of the compounds object of the present invention in HDPE plates.

I granuli di HDPE ottenuti come sopra descritto nell'Esempio 2, vengono sottoposti a stampaggio ad iniezione, per 3 minuti a 260°C, ottenendosi placchette aventi uno spessore di 1 mm. The HDPE granules obtained as described above in Example 2 are subjected to injection molding for 3 minutes at 260 ° C, obtaining plates having a thickness of 1 mm.

Le placchette così ottenute vengono sottoposte ad invecchiamento in stufa ("oven ageing") a 120°C e viene misurato il tempo di sbriciolamento ("embrìttlement time"): i risultati ottenuti vengono riportati in Tabella 2. The plates thus obtained are subjected to aging in an oven ("oven aging") at 120 ° C and the crumbling time ("embrittlement time") is measured: the results obtained are reported in Table 2.

TABELLA 2 TABLE 2

ESEMPIO 4 EXAMPLE 4

Valutazione della attività stabilizzante dei composti oggetto della presente invenzione in placchette di polipropilene. Evaluation of the stabilizing activity of the compounds object of the present invention in polypropylene plates.

Operando come sopra descritto negli Esempi 2 e 3, vengono preparate placchette di polipropilene commerciale . By operating as described above in Examples 2 and 3, commercial polypropylene plates are prepared.

Le suddette placchette vengono sottoposte ad invecchiamento in stufa ("oven ageing") a 120°C e viene misurato il tempo di sbriciolamento ("embrittlement time"): i risultati ottenuti vengono riportati in Tabella 3. The aforementioned plates are subjected to aging in an oven ("oven aging") at 120 ° C and the crumbling time ("embrittlement time") is measured: the results obtained are reported in Table 3.

TABELLA 3 TABLE 3

ESEMPIO 5 EXAMPLE 5

Dati termogravimetrici. Thermogravimetric data.

Mediante analisi termogravimetrica, in atmosfera inerte di azoto, viene confrontata la stabilità termica del composto (A) con quella del composto (B): i risultati ottenuti vengono riportati in Tabella 4 (viene riportata la % di perdita in peso in funzione della temperatura). By means of thermogravimetric analysis, in an inert atmosphere of nitrogen, the thermal stability of compound (A) is compared with that of compound (B): the results obtained are reported in Table 4 (the% of weight loss as a function of temperature is reported) .

TABELLA 4 TABLE 4

Claims

CLAIMS 1. Stabilized polymer compositions comprising: a polyolefin; and at least one antioxidant compound of the thio-phenolic type having general formula (I):

in which: n represents an integer between 1 and 100 inclusive; R represents a hydrogen atom; or a group having general formula (II):

wherein R1 represents a linear or branched C1-C3 alkyl group; Z represents an OH group; or a group having formula (III):

or, R and Z jointly represent a direct bond giving rise to cyclic structures; Y represents a group having general formula (IV):

wherein R1 represents a linear or branched C1-C3 alkyl group.

2. Stabilized polymeric compositions according to claim 1, wherein the polyolefins are selected from the thermoplastic resins.

3. Stabilized polymeric compositions according to claim 2, wherein the thermoplastic resins are homopolymers or copolymers obtained from two or more comonomers, or mixtures of two or more of said polymers.

4. Stabilized polymeric compositions according to claim 3, wherein the monomers useful in the production of the aforesaid homopolymers and copolymers have from 2 to 20 carbon atoms, preferably from 2 to 12 carbon atoms.

5. Stabilized polymeric compositions according to claim 4, wherein the monomers are the α-olefins such as, ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene; unsaturated esters such as, vinyl acetate, ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, and other alkyl acrylates; diolefins such as 1,4-pentadiene, 1,3-hexadiene, 1,5-hexadiene, 1,4-octadiene and ethylene-norbornene which is usually the third monomer in terpolymers; other monomers such as, styrene, p-methyl styrene, α-methyl styrene, p-chloro styrene, vinyl naphthalene, and similar arylolefins; nitriles such as, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile; vinyl methyl ketone, vinyl methyl ether, vinylidene chloride, maleic anhydride, vinyl chloride, vinyl alcohol, tetrafluoroethylene, chlorotrifluoroethylene; acrylic acid, methacrylic acid, and other similar unsaturated acids.

6. Stabilized polymeric compositions according to claim 3, wherein the homopolymers and copolymers are non-halogenated, or conventionally halogenated, generally with chlorine and bromine.

7. Stabilized polymeric compositions according to claim 3, wherein the homopolymers or copolymers are the homopolymers and copolymers of ethylene and propylene, both in non-halogenated and in halogenated form; terpolymers such as ethylene / propylene / diene monomer-based rubbers.

8. Stabilized polymeric compositions according to claim 7, wherein the ethylene-based polymers are the following: high pressure homopolymer of ethylene; copolymer of ethylene and one or more α-olefins having from 3 to 12 carbon atoms; homopolymer or copolymer of ethylene having a hydrolyzable silane function grafted to their structure; copolymer of ethylene and an alkenyl trialkoxy silane such as trimethoxy vinyl silane; or a copolymer of an α-olefin having from 2 to 12 carbon atoms and an unsaturated ester having from 4 to 20 carbon atoms such as ethylene / ethyl acrylate or vinyl acetate copolymer; ethylene / ethyl acrylate or vinyl acetate / hydrolysable silane terpolymer; ethylene / ethyl acrylate or vinyl acetate copolymers having a hydrolyzable silane function grafted to their structure.

9. Stabilized polymeric compositions according to claim 7, wherein the polypropylene-based polymers are: homopolymers and copolymers of propylene and of one or more α-olefins such as, homopolymers and copolymers of propylene and of one or more α-olefins in which the part of the copolymer based on the polypropylene is at least 60% by weight of the total weight of the copolymer.

10. Stabilized polymeric compositions according to claim 2, wherein the thermoplastic resins are cross-linked.

11. Stabilized polymeric compositions according to any one of the preceding claims, in which the antioxidant compound having general formula (I) is used in combination with other conventional additives.

12. Use of the stabilized polymeric compositions of any one of the preceding claims, as insulating material in electric wires and cables.

13. Electric wires and cables coated with the polymeric compositions of any one of the preceding claims.