PL204096B1 - Stabilised cable insulation composition for telecommunication cables - Google Patents

Abstract

FIELD: insulating materials for telecommunication cables. ^ SUBSTANCE: polyolefin insulation of conductors in hydrocarbon lubricant filled telecommunication cable which is then placed in junction box operating in the open is susceptible in particular to adverse impact of heat, oxygen, and moisture. In order to ensure reliable functioning of these conductors under mentioned conditions, use can be made of combination of one or more primary phenolic antioxidants chosen from N,N'-hexane-1.6-diilbis-(3(3.5-di-tertiary-butyl-4-hydroxyphenylpropionamide)), tris(3.5-di-tertiary-butyl-4-hydroxybenzyl)isocyanin-rhata, and tris(2-(3.5-di-tertiary-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl)isocyanourate together wit one or more alkyl hydroxyphenyl alkanoylhydrazine metal deactivators. ^ EFFECT: enhanced oxidation resistance of polyolefin insulation of conductors. ^ 8 cl, 1 tbl, 1 ex

Description

The present invention relates to a stabilized telecommunications cable structure. More particularly, the embodiment relates to a polyolefin composition applicable to wire and cable insulation that has improved resistance to the detrimental effects of heat, oxygen and moisture. The stabilized compositions are suitable for use in telecommunications cables.

A typical telecommunications cable is constructed of twisted pairs of polyolefin insulated copper wires that are coiled together and protected by a cable sheath. The cable jacket is comprised of foil and / or armor in combination with the polymeric material of the jacket. The entire system is called a "telecommunications cable."

In order to reduce the risk of water penetrating into the cable system and minimize the harmful effects of moisture on the polyolefin insulation, the system is made watertight by filling the voids in the cable with a hydrophobic lubricant. Cable systems of this type are disclosed, for example, in U.S. Pat. No. 3,888,709, 4,044,200, 4,218,577, 5,502,288 and European Patent Application 565,868 A2, and references cited therein. The grease filling the cable, as is known, extracts the stabilizers contained in the cable insulation. This is discussed, for example, in Plastics Additives Handbook, Ed. 3rd, R. Gachter, H. Mler, ed., Hanser Publishers, pages 116-119 (1990).

Connecting two or more telecommunications cables is often necessary and is done in an external housing called a rack or junction box. Inside the rack, the cable sheath is removed, the cable filling grease is wiped off, and the conductive cables are connected as required. The exposed insulated wires are therefore exposed to the unfavorable conditions of heat, oxygen and moisture. Polyolefin insulation, after losing some of its stabilizers extracted by the filler lubricant, is particularly susceptible to damage by environmental conditions and can show premature oxidative damage. This damage manifests itself in the loss of the physical properties of the insulation, which ultimately leads to a loss of electrical conduction efficiency.

It is known to stabilize polyolefin wire insulation in telecommunications applications with sterically shielded phenolic antioxidants. The prior art system comprises the use of sterically shielded phenol in combination with a metal deactivator such as Irganox® MD 1024, 1,2-bis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine or Naugard® XL-1 , 2,2'-oxalyldiamido-bis- [ethyl-3- (3,5-di-tert-butyl-4-hydroxylphenyl) propionate]. A typical stabilizer package contains as the primary antioxidant, Irganox® 1010, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and as a metal deactivator, Irganox® MD 1024. This system is disclosed in European Patent Application 565,868 A2 and US Patent Specification No. 4,044,200, 5,380,591 and 5,575,952. Irganox® is a protected trademark of Ciba Specialty Chemicals Corp., Naugard® is a protected trademark of Uniroyal.

U.S. Patent Description No. 4,044,200 discloses the stabilization of a polyolefin wire insulation in the presence of a moisture barrier filler in combination with an alkylhydroxyphenylalkanoylhydrazide and / or substituted amidotriazole together with a high molecular weight sterically shielded phenolic antioxidant. Specifically disclosed is a combination of Irganox® MD 1024 and Irganox® 1010.

U.S. Patent Description No. 4,812,500 discloses a polyolefin composition with improved resistance to hot oxygenated water, chlorinated water and UV radiation. The composition includes a sterically shielded amine as a UV stabilizer, a sterically shielded phenolic heat stabilizer, and a chelating (metal deactivating) agent. The sterically shielded phenolic compound is selected from the specific group consisting of Irganox® 1010, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and Irganox® 3114, tris (3,5-di isocyanurate) -tert-butyl-4-hydroxybenzyl). The chelating agent is selected from the group consisting of Irganox® MD 1024, 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine. Irganox® is a trademark of Ciba Specialty Chemicals Corp. It is contemplated as the invention is applicable to a variety of systems where water or moisture is present, including wire and cable sheaths. There is no mention of cable filling systems with grease, where there is a possibility of extracting additives.

U.S. patents Nos. 5,380,591, 5,453,322, 5,575,952, 5,766,761, and 5,807,635 disclose the stabilization of hydrocarbon-filled telephone cables by combining an alkylhydroxyphenylalkanoylhydrazine mixture with a functionalized amine sterically shielded. Specifically, Irganox® MD 1024 is disclosed as the hydrazine in each case.

U.S. Patent Description 5,474,847 describes the stabilization of polyolefin wire insulation in grease-filled telephone cables by the reaction products of hydrazide derivatives of sterically shielded phenols or sterically shielded amines or amine derivatives of sterically shielded amines with quinones.

U.S. Patent Description 5.502.288 discloses the stabilization of polyolefin wire insulation in telephone cables using Irganox® MD 1024 or Naugard® XL-1, or mixtures thereof with selected antioxidants.

European Patent Application 565,868 A2 teaches the stabilization of polyolefin wire insulation compositions exposed to water-blocking fillers by combining a divalent metal salt and phenolic carboxylic or phosphonic acid with a metal deactivator. Specifically mentioned metal deactivators are Irganox® MD 1024 and Naugard® XL-1. A preferred composition also includes the use of Irganox® 1010.

WO 93/24935 teaches the use of reaction products of an unsaturated aliphatic diacid anhydride with one or more functionalized, sterically shielded amines and / or sterically shielded phenols to stabilize polyolefin wire insulation in grease filled telephone cables.

WO 93/24938 discloses a grease-filled cable structure in which a polyolefin wire insulation is bonded thereto with an aliphatic diacid anhydride, one or more sterically shielded functionalized amines, and / or functionalized sterically shielded phenols.

In order to protect the polyolefin wire insulation that is exposed to the environmental conditions in the junction box, and to prevent the stabilizers from being extracted by the cable filling grease, it has been suggested that high concentrations of the stabilizer system should be used. There is a need to find more effective primary antioxidant / metal deactivator combinations than those of the prior art to lower the high cost associated with such stabilizer concentrations. The effectiveness of the stabilizer in this context is the combined ability of the stabilizer system to prevent extraction from the polyolefin wire insulation into the cable filling lubricant and to provide a polyolefin resistant to the harmful effects of heat, oxygen and moisture.

It has surprisingly been found that a combination of one or more major antioxidants selected from: Irganox® 1098, N, N'-hexane-1,6-diylbis- (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)) , Irganox® 3114, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and Irganox® 3125, tris (2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl) isocyanurate, together with one or more alkylhydroxyphenylalkanoylhydrazine metal deactivators is particularly effective for providing oxidative stability to polyolefin wire insulation in grease filled telecommunications cables. Irganox® is a trademark of Ciba Specialty Chemicals Corp.

The present invention relates to a new construction of a hydrocarbon grease filled cable in which the polyolefinic insulation has improved oxidative stability.

The subject of the invention is a stabilized structure of a telecommunications cable comprising a plurality of insulated electrical conductors (i) with spaces between them, (ii) a hydrocarbon lubricant filling of the cable within the spaces, a sheath surrounding components (i) and (ii), characterized in that the insulation comprises :

(a) one or more polyolefins, and (b) one or more major antioxidants selected from the group: N, N'-hexane-1,6-diylbis- (3- (3,5-di-tert-butyl-4 -hydroxyphenylpropionamide)), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and tris (2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl) isocyanurate, and (c) one or more metal deactivators selected from alkylhydroxyphenylalkanoylhydrazines, wherein the antioxidants of component (b) in total are present in an amount ranging from about 0.05 wt.%. % to about 1.0 wt.% based on the weight of the polyolefin of component (a), the metal deactivators of component (c) are collectively present in an amount ranging from about 0.1 wt.%. % to about 2.0 wt.% based on the weight of the polyolefin of component (a).

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Preferably, said polyolefins of component (a) are polyethylene or polypropylene or mixtures thereof. Preferably, the metal deactivators of component (c) are compounds of formula

where n is 0 or an integer from 1 to 5;

R1 is a linear or branched alkyl chain having 1 to 6 carbon atoms; R2 is hydrogen or R1; and

R3 is hydrogen, an alkanoyl having 2 to 18 carbon atoms or a group of the formula

wherein n, R1 and R2 are independently defined as above.

Preferably, the metal deactivator of component (c) is 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine. Preferably, the hydrocarbon cable filler lubricant of component (ii) or one or more hydrocarbon components thereof is present in the polyolefin of component (a). Preferably, the hydrocarbon cable filler lubricant of component (ii) or one or more hydrocarbon components thereof, in total, is present in the polyolefin of component (a) in an amount ranging from about 3 to about 30 weight percent based on the weight of component (a).

The polyolefins in component (a) are generally cross-linked thermoplastic resins. They can be homopolymers or copolymers made from two or more comonomers, or a blend of two or more of these polymers, typically used as film, sheet or tube, and as sheath and / or insulating materials in wire and cable applications. The monomers useful in the preparation of these homopolymers and copolymers can have 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms. Examples of such monomers are alpha-olefins such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 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 ethylidene norbornene, usually the third monomer in the terpolymer; other monomers such as styrene, p-methylstyrene, alpha-methylstyrene, p-chlorostyrene, vinylnaphthalene, and similar aryl olefins; nitriles such as acrylonitrile, methacrylonitrile, and alpha-chloroacrylonitrile; methyl vinyl ketone, vinyl methyl ether, vinylidene chloride, maleic anhydride, vinyl chloride, vinylidene chloride, vinyl alcohol, tetrafluoroethylene and chorotrifluoroethylene; and acrylic acid, methacrylic acid, and other similar unsaturated acids.

The cited homopolymers and copolymers may be unhalogenated or halogenated in the usual manner, generally with chlorine or bromine. Examples of halogenated polymers are polyvinyl chloride, polyvinylidene chloride, and polytetrafluoroethylene. Ethylene and propylene homopolymers and copolymers are preferred, in both unhalogenated and halogenated forms. Included in this preferred group are terpolymers such as ethylene / propylene / diene monomer rubbers.

Other examples of ethylene polymers are as follows: high pressure ethylene homopolymer; a copolymer of ethylene and one or more alpha-olefins having 3 to 12 carbon atoms; an ethylene homopolymer or copolymer having a hydrolysable silane grafted onto the backbone; a copolymer of ethylene and an alkenyltrialkoxysilane such as trimethoxyvinylsilane; or an alpha-olefin copolymer having 2 to 12 carbon atoms and an unsaturated ester having 4 to 20 carbon atoms, e.g. ethylene / ethyl acrylate or vinyl acetate copolymer; ethylene / ethyl acrylate or vinyl acetate / silane terpolymer

Hydrolysable; ethylene / ethyl acrylate or vinyl acetate copolymers having a hydrolysable silane grafted onto their backbones.

With regard to polypropylene; homopolymers and copolymers of propylene and one or more alpha-olefins in which the proportion of the propylene-based copolymer is at least about 60 percent by weight based on the weight of the copolymer may be used to provide the polyolefin of the invention. Preferred alpha-olefinic propylene comonomers are those having 2 or 4 to 12 carbon atoms.

Polyolefins, i.e. polymers of the monoolefins mentioned above, for example polyethylene or polypropylene, can be obtained by other, in particular the following methods, such as:

1) radical polymerization (usually under high pressure and elevated temperature);

2) catalytic polymerization using catalysts which usually contain one or more of the metals of groups IVb, Vb, VIb or VIII of the periodic table. These metals typically have one or more ligands, typically oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be p- or s-coordinated. These metal complexes can be in free form or fixed to supports, usually activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may be used as such for the polymerization, or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxides, said metals being elements of groups Ia, IIa and / or IIIa of the periodic table. The activators may be suitably modified with further ester, ether, amine or silyl ether groups. These catalyst systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene, or monocenter catalysts (SSC).

The homopolymer or copolymers may be cross-linked or cured with an organic peroxide, or may be grafted with an alkenyltrialkoxysilane to render it hydrolysable in the presence of an organic peroxide which acts as a free radical generator or catalyst. Useful alkenyltrialkoxysilanes include vinyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltriisopropoxysilane. The alkenyl and alkoxy radicals can have 1 to 30 carbon atoms, and preferably have 1 to 12 carbon atoms. The hydrolysable polymers can be cured with moisture in the presence of a silanol condensation catalyst such as dibutyl tin dilaurate, dioctyl tin maleate, stannous acetate, stannous octanoate, lead naphthenate, zinc octanoate, iron 2-ethyl hexanoate and other metal carboxylates.

Ethylene homopolymers or copolymers where ethylene is the major comonomer and propylene homopolymers and copolymers where propylene is the major comonomer may be cited herein as polyethylene and polypropylene, respectively.

The polyolefins of component (a) are preferably polyethylene or polypropylene, or mixtures thereof.

Alkylhydroxyphenylalkanoylhydrazines of component (c) are disclosed in U.S. Patent No. No. 3,660,438 and 3,773,722. Preferably the compounds of component (c) have the following structure:

where n is 0 or an integer from 1 to 5;

R1 is a straight or branched alkyl having 1 to 6 carbon atoms; R2 is hydrogen or R1; and

R3 is hydrogen, an alkanoyl of 2 to 18 carbon atoms or a group of the formula

Wherein n, R1 and R2 are independently not defined the same as above.

The radical R2 is preferably ortho to the OH group.

Preferably the metal deactivator of component (c) is Irganox® MD 1024, 1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, Ciba Specialty Chemicals Corp.

The hydrocarbon lubricant in the cable of component (ii) is a mixture of hydrocarbon compounds that is semi-solid at service temperatures. It is known in the industry as the "cable filler compound." A typical requirement for a cable filler compound is that minimal grease leakage from the cut cable end at 60 ° C or above the rated temperature. Another common requirement is that the lubricant protects against water ingress in the short section of the cut cable when pressurized water is applied at one end. Among other common requirements is cost competitiveness; minimized harmful effects on signal transmission; minimized effects on the physical characteristics of polymer insulation and cable sheath materials; thermal and oxidative stability; and processability in making the cable.

Fabrication of the cable can be accomplished by heating the cable filler compound to a temperature of approximately 100 ° C. This liquefies the filler compound so that it can be pumped into the multi-conductor cable core to fully impregnate the gaps and remove air spaces completely. Alternatively, thixotropic cable filler compounds using shear induced flow may be processed at reduced temperatures in the same manner. A typical finished, grease-filled, conductive cable has a cross section of about 52 percent of insulated wire and about 48 percent of spacing in terms of total cross-sectional areas. Since the gaps are completely filled with the cable filler compound, the filled cable core typically contains about 48 volume percent of the cable filler compound.

The cable filler compound or one or more of its hydrocarbon components penetrate the insulation by absorption from between the spaces. Generally, the insulation absorbs up to about 3 to about 30 weight percent of the cable filler compound or one or more of its hydrocarbon components in total, based on the weight of the polyolefin insulation. Typical absorption is in the range of about 5 to about 25 weight percent based on the weight of the polyolefin. The cable filling compound generally comprises hydrocarbons of varying molecular weights. Polyolefin cable filler compound absorption or swelling is preferred for the lower molecular weight components of the cable filler compound. This swelling of the polyolefin insulation leads to the migration of additives from the cable insulation to the cable filling compound as discussed above. The presence of the cable filler compound therefore represents an additional obstacle to stabilizing the polyolefin insulation.

Examples of hydrocarbon cable filling grease (cable filling compound) are petroleum jelly; petroleum jelly / polyolefin wax mixtures; oil-modified thermoplastic rubbers (ETPR or filled thermoplastic rubbers); paraffin oil; naphthenic oil; mineral oil; the aforesaid oils thickened with asphalt oil, petroleum jelly or wax; polyethylene wax; mixture of mineral oil / rubber block copolymer; lubricating grease; and various mixtures thereof, all of which meet industrial requirements similar to those disclosed above.

In addition to preventing the extraction of antioxidants, the wire insulation formulation must withstand any possible destabilizing effect of the absorbed components from the cable filler compound. In addition, the stabilization package must counteract the copper wire, which is a potential catalyst for the oxidative degradation of olefins, and must also counteract the residual air entraining chemicals found in cellular and cellular / solid (foam / coating) foamed polymer insulations.

In addition to components (b) and (c), the insulation in the cable structure according to the present invention may contain further co-stabilizers (additives) such as, for example, the following.

1. Antioxidants

1.1. Alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2 , 6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which have linear or branched side chains, for example 2,6-di- nonyl-4-methylphenol, 2,4-dimethyl-6- (1-methyloundec-1-yl) phenol, 2,4-dimethyl-6- (1-methylheptadec-1-yl) phenol, 2,4-dimethyl- 6- (1-methyltridec-1-yl) phenol and mixtures thereof.

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1.2. Alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2.4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol,

2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl- 4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl adipate) ).

1.4. Tocopherols, e.g. a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3 -methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylphenol), 4,4'-bis (2, 6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, e.g. 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl -6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis ( 4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2 '-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenzyl (2,6- di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6 -bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- ethylene glycol bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, bis [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate], bis (3- tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'tert-butyl-2-hydroxy-5-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane , 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n- dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl, 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, octadecyl ether, 4- hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate tridecyl, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiotherephthalate , bis- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonates, e.g. dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) ) malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2, 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, e.g. 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis- (3,5-di -tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Triazine compounds, for example 2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis ( 3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine,

2-octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl -4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris isocyanurate (4-tert -butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5 -tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzylphosphonates, e.g. dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate,

Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, monoethyl acid calcium salt 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13. Esters of b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

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1.14. E- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid esters with mono- or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15. E- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid esters with monohydric or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2 -propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide,

3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16. 3,5-di-tert-butyl-4-hydroxyphenylacetic acid esters with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide,

3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. Amides of b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N ' -bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2 - (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C).

1.19. Amine antioxidants, e.g. N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine , N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl- N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl -2-naphthylamine, octylated diphenylamine,

-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol,

4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-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, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono and dialkylated tert-butyl / tert-octylphenothiazines , a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6, 6-tetramethyl-piperid-4-yl-hex amethylene diamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilizers.

2.1. 2- (2-Hydroxyphenyl) benzotriazoles, e.g. 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (5-tert- butyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) - 5-chloro-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chloro-benzotriazole, 2- (3-sec-butyl-5-tert-butyl-2-hydroxyphenyl) benzotriazole , 2- (2-hydroxy-4-octyloxyphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-bis-a, α-dimethylbenzyl) -2 -hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-octyloxycarbonyletyl) phenyl) -5-chloro-benzotriazole, 2- (3-tert-butyl-5- [2- (2 -ethylhexyloxy) carbonylethyl] -2-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3 -tert-butyl-2 e.g. p, p'-di4-nonanoylaminophenol,

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-hydroxy-5- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3-tert-butyl-5- [ 2- (2-ethylhexyloxy) carbonylethyl] -2-hydroxyphenyl) benzotriazole, 2- (3-dodecyl-2-hydroxy-5-methylphenyl) benzotriazole, 2- (3-tert-butyl-2-hydroxy-5- (2 -isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene bis [4- (1,1,3,3-tetraethylbutyl) -6-benzotriazol-2-ylphenol]; transesterification product 2- [3-tert-butyl- 5- (2-methoxycarbonyl-yl) -2-hydroxyphenyl] -2H-benzotriazole polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2] -2, where R = 3'-tert-butyl-4'-hydroxy- 5'-2H-benzotriazol-2-ylphenyl, 2- [2-hydroxy-3- (α, α-dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2- hydroxy-3- (1,1,3,3-tetramethylbutyl) -5- (α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the derivatives: 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-4.4 '-dimethoxy.

2.3. Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4 2,4-di-tert-butylphenyl-hydroxybenzoate,

Hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4.6 3,5-di-tert-butyl-4-hydroxybenzoate -di-tert-butylphenyl. ,

2.4. Acrylates, e.g., ethyl a-cyano, e-diphenylacrylate, a-cyano-e, isooctyl e-diphenylacrylate, methyl a-carbomethoxycinnamate, methyl α-cyano-e-methyl-p-methoxy cinnamate, α-cyano- butyl e-methyl-p-methoxy cinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N-carbomethoxy-e-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, for example complexes of nickel and 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as a 1: 1 or 1: 2 complex with or without additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, e.g. 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid methyl or ethyl ester, nickel and 2-ketoxime complexes, e.g. hydroxy-4-methylphenyl undecylketoxime, nickel and 1-phenyl-4-lauroyl-5-hydroxypyrazole complexes, with or without additional ligands.

2.6. Sterically shielded amines, e.g. bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2, 6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4- bis (1,2,2,6,6-pentamethyl-4-piperidyl) hydroxybenzylmalonate, a condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris- (2, 2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1'- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis - (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7, 7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy- 2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholine-2,6-dichloro -1,3,5-triazine, a condensation product of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2- bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine condensation product 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) pyrrolidin-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 N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-di chloro-1,3,5-triazine, a condensation product of 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-oxa-3,8-diaza-4-oxospiro [4,5] decane, reaction product 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa- 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-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethylene malonic acid diester with 1,2,2,6,6- pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, reaction product of a copolymer without

Maleic acid hydride and alpha-olefin with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamide, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxyanilide, 2,2'-didodecyloxy-5,5'-di- tert-butoxyanilide, 2-ethoxy-2'-ethyloxyanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and its mixture with 2-ethoxy-2 ' -ethyl-5,4'-di-tert-butoxyanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-Hydroxyphenyl) -1,3,5-triazines, e.g. 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 , 3,5triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) - 4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5- triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3 -butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -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-hexyl oxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6- tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1, 3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropoxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 4,6-bis (2,4-dimethylphenyl) -2- [2-hydroxy-4- (2-hydroxy-3-nonyloxypropoxy) -5- (1-methyl-1-phenylethyl) phenyl ] -1,3,5-triazine.

3. Metal deactivators, e.g. N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine,

N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine,

3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacooyl-bisphenylhydrazide, N, N'-diacetyl-adipoyl-dihydrazide, N, N'-bis (salalicyloyl) dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, di-diphenylpentaerythritol diphosphite, di-diphosphorythritol di-diphosphite bis (2,4-di-tert-butylphenyl) pentaerythritol, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6) diphosphite -methylphenyl) pentaerythritol, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitan triphosphite, tetrakis (2,4-di-tert-butylphenyl) diphosphite, 6-isooctyloxy-2, 4,8,10-tetra-tert-butyl-dibenzo [d, f] [1,3,2] dioxaphosphepine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo [d, g ] [1,3,2] dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 2,2 ' , 2-nitrile [triethyltris (3.3 ', 5.5'-tetr a-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl- 2,2'-diyl) phosphite.

The following phosphites are particularly preferred:

tris (2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba Specialty Chemicals Corp.), tris (nonylphenyl) phosphite,

PL 204 096 B1

5. Hydroxylamine, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-diheoxadecylhydroxylamine, N, N-dihexadecylhydroxylamine hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine, a derivative of hydrogenated tallowamine, N, N-di (alkyl) hydroxylamine produced by direct oxidation of N, N-di (hydrotalline).

6. Nitrons, for example N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl- alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-pentadecyl nitrone, N-heptadecyl-alpha- heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N, N-dialkylhydroxylamine of a hydrogenated tallamine derivative.

7. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3 - [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2- one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl- benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl) -5.7- di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

8. Thiosynergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

9. Peroxide scavengers, for example esters of b-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters of mercaptobenzimidazole or zinc salt

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2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (b-dodecyl mercapto) propionate.

10. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

11. Basic co-stabilizers, e.g. melamine, polyvinylpyrrolidone, di-cyanediamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts and higher fatty acids, e.g. calcium stearate, stearate zinc, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

12. Crystallization centers, for example inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulphates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, e.g. tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).

13. Fillers and structural strengthening agents, 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 other products flour and fibers natural, synthetic fibers.

14. Other additives, e.g. plasticizers, lubricants, emulsifiers, pigments, dyes, optical brighteners, rheology additives, catalysts, flow regulating agents, lubricants, cross-linking agents, cross-linking aids, halogen scavengers, smoke inhibitors, flame retardants, antistatic agents, clarifying agents and blowing agents.

Fillers (item 13 in the list) are, for example, metal hydroxides, especially magnesium hydroxide and aluminum hydroxide. They may be added in an amount of about 0.01 to 60 percent by weight based on the weight of the polyolefin.

Blowing agents (entry 14), such as azodicarbonamide, may be used to provide foam rather than solid insulation.

The major antioxidants of component (b), metal deactivators of component (c) and possible further additives are attached to the polyolefin of component (a) by known methods, e.g. before or after molding, or also by applying a dissolved or dispersed stabilizing mixture to the polyolefin, with or without solvent evaporation.

Components (b) and (c), and optionally further additives, may also be added to the polyolefin in the form of a masterbatch that contains these components at a concentration of, for example, from about 2.5 percent to about 25 percent by weight.

The antioxidants of component (b) in total are used, for example, in the range of from about 0.01 weight percent to about 1.5 weight percent based on the weight of the polyolefin (a). Preferably, compounds of component (b) in total are used in the range of from about 0.05 weight percent to about 1.0 weight percent based on the weight of the polyolefin (a).

Component (c) metal deactivators in total are used in the range of from about 0.1 weight percent to about 2.5 weight percent based on the weight of the polyolefin (a). Preferably, compounds of component (c) in total are used in the range of from about 0.1 weight percent to about 2.0 weight percent based on the weight of the polyolefin (a).

The weight ratio of the metal deactivators of component (c) to the antioxidants of component (b) used in the present invention is, e.g., in the range from about 0.5: 1 to about 20: 1. Preferably, the ratio of component (c) to component (b) ranges from about 1: 1 to about 10: 1.

The following examples illustrate the invention in more detail. However, they should not be considered as limiting the scope of the invention in any way.

Example 1: Stabilization of polyolefins in a grease-filled cable structure

One hundred parts high-density polyethylene is dry blended with 0.4 parts Irganox® MD 1024 (1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine) and 0.2 parts of one of the major antioxidants summarized in Table 1 below. The mixtures were pelleted at 230 ° C in a Superior / MPM extruder using a 224: 1 L / D screw with a Maddock mixer head at 60 rpm.

The pelletized polyethylene containing the stabilizing mixtures was compression molded at 204 ° C (400 ° F) into 0.254 mm (0.01 inch) thick films with a Mylar substrate. The "Initial Oxidation Induction Period (OIT)" was measured for these films.

PL 204 096 B1

The foil samples were immersed in Witcogel®, available from Witco, a typical hydrocarbon cable filler grease used in telecommunications cables. The Witco filler compound contains 0.6% Irganox® 1035, thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. The film samples immersed in the filler compound were placed in an air dryer at 70 ° C for 14 days. The samples were then wiped clean with the cable filling grease. The "oxidation induction period after aging" was measured for these samples.

The OIT study was performed using a differential scanning calorimeter as per ASTM D3895 Standard Test Method. The test conditions are as follows: uncrimped aluminum shell, no screen; heating to 200 ° C under nitrogen; then changing to an oxygen flow of 100 milliliters / minute. The Oxidation Induction Period (OIT) is the period between the onset of oxygen flow and the exothermic decomposition of the test sample. OIT is reported in minutes; the longer the OIT, the more effectively the stabilizing mixture prevents oxidative degradation. The relative efficiencies of stabilizing mixtures as applied to grease filled cables can be predicted by comparing the initial OIT and OIT values after aging.

T a b l i c a 1

The main antioxidant Initial ICU (min.) After aging (min.) Irganox® 1010 77 25 Irganox® 1098 161 90 Irganox® 3114 91 44 Irganox® 3125 126 51

Stabilizing mixtures Irganox® 1098, Irganox® 3114, Irganox® 3125, each with a metal deactivator Irganox® MD 1024 (1,2-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine), exceeding the action of the mixture prior art stabilizer Irganox® 1010 / Irganox® MD 1024 in the initial ICU and after aging. Irganox® 1098 is N, N'-hexane-1,6-diylbis- (3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)), Irganox® 3114 is tris (3,5-di- tert-butyl-4-hydroxybenzyl), Irganox® 3125 is tris (2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl) isocyanurate. Irganox® is a trademark of Ciba Specialty Chemicals Corporation.

Claims (3)

1. A stabilized telecommunications cable structure comprising a plurality of insulated electrical conductors (i) with spaces between them, (ii) a hydrocarbon lubricant filling of the cable within the spaces, a sheath surrounding components (i) and (ii) characterized in that the insulation comprises ( a) one or more polyolefins, and (b) one or more major antioxidants selected from the group: N, N'-hexane-1,6-diylbis- (3- (3,5-di-tert-butyl-4- hydroxyphenylpropionamide)), tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and tris (2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl) isocyanurate, and (c) one or more metal deactivators selected from alkylhydroxyphenylalkanoylhydrazines, wherein the antioxidants of component (b) in total are present in an amount ranging from about 0.05 wt. % to about 1.0 wt.% based on the weight of the polyolefin of component (a), the metal deactivators of component (c) in total are present in an amount in the range of about 0.1 wt.%. % to about 2.0 wt.% based on the weight of the polyolefin of component (a). 2. Cable structure according to claim The method of claim 1, characterized in that said polyolefins of component (a) are polyethylene or polypropylene or mixtures thereof. 3. Cable structure according to claim The process of claim 1, wherein the metal deactivators of component (c) are compounds of formula