SK40397A3 - A composition containing polyolefin with residue of catalysts, trialkanolamine-triphosphite as stabilizer and method for stabilizing polyolefins - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition capable of preventing the deterioration caused by oxidation, heat and light, excellent in stability and corrosion resistance and useful for molding products, etc., by including a specific polyolefin and a specified trialkanolamine trisphosphite therein. SOLUTION: This composition comprises (A) a polyolefin such as polypropylene or polyethylene containing a residue of one or more transition metals such as aluminum, boron, titanium, zirconium, chromium or vanadium, main-group metals or a mixture thereof used as a (co)catalyst capable of causing the polymerization of the polyolefin in an amount of 10-1000ppm and (B) a stabilizing effective amount of a compound represented by the formula [(n) is 0 or 1; Q is a direct bond, S, etc.; Y1 to Y6 and Z1 to Z6 are each H, a 1-18C alkyl, etc.; A1 to A3 are each a 1-18C alkylene, etc.]. Furthermore, the component B is used in an amount of preferably 0.01-5wt.% based on the weight of the component A and a phenolic antioxidant, a light stabilizer or a processing stabilizer is preferably additionally formulated therein.

Description

Technical field

The invention relates to polyolefins containing catalyst residues which are stabilized using trialkanolamine triphosphites.

BACKGROUND OF THE INVENTION

Approximately between 1930 and 1950, polyethylene was produced using a high-pressure free-radical method in the liquid phase (R.V. Raff and J. B. Allison, Polyethylene, Interscience, New York (1956)). During the 1850s, it was found that ethylene can be polymerized using transition metal complexes as homogeneous or heterogeneous catalysts. Thus, several types of homopolymer polyethylene have been obtained (K. Ziegler et al. Angew. Chem., 67, 541 (1955); J. P. Hogan et al., Belgian Patent No. 530,617 (January 24, 1955).

D. James, Encyclopedia of Polymer Science and Engineering, 1st edition, Wiley Interscience, New York, Vol. 6, 1986, p. 429; and D.L. Beach et al., Detto p. 454). Soon after, stereoregular polypropylene was invented (G. Natta et al., J. Am. Chem. Soc., 37, 1708 (1955), RB Lieberman, Encyclopedia of Polymer Science and Engineering, 1st edition, Wiley Interscience, New York, Vol. 13, 1986, p. 429, and P. Pino et al., Angew. Chem. Irit. Ed. Engl., 19, 857 (1980).

There have been many breakthroughs in the field of polymerization research and technology over the past forty years (P. Locatelli, Trends in Poly. Sci., 3, 87 (1994)). Today, there are a wide variety of different types of polyolefin homopolymers and copolymers. There are many methods of polymerization based on liquid phase, suspension, v

gas phase or bead polymerization (D. James, supra; D. L. Beach et al., supra; R.B. Lieberman, supra; and P. Pino et al., supra). There is also a wide variety of transition metal catalyst groups, such as titanium, vanadium, chromium, and zirconium, for olefin polymerization reactions. Various co-catalysts based on alkylaluminium compounds are also known. Catalyst supports, stereospecificity control agents and promoters are key reagents used to improve the rate and stereoregularity obtainable in a polymerization reaction (M. Farina, Trends in Poly. Sci., 3, 80 (1994)).

Perhaps one of the most interesting advances in the field of olefin polymerization catalysis is the onset of single site catalysis (SSC) using metallocene compounds (W. Kaminsky, Catal. Today, 20, 257 (1994)). This relatively new field of polymerization chemistry is based predominantly on previously known transition metal catalysts such as titanium and zirconium, along with co-catalysts based on alkylaluminium compounds, aluminoxanes or anionic non-coordinating boron compounds (AD Horton, Trend in Poly. Sci., 2, 158 (1994)).

At the beginning of transition metal catalysed olefin polymerization, considerable efforts were made to deactivate catalyst residues (D. James, supra; and R.B. Lieberman, supra). Removal or deactivation of the catalyst was considered necessary because the amounts of residual catalysts were high and were found to have a significant adverse effect on the final stability of the polymer.

In the past, one method of deactivating the catalyst was to add aqueous or alcoholic base solutions to the polymerization reaction mixture followed by an intensive wash to remove the solubilized deactivated catalyst. Another procedure used in the case of solution polymerization was to remove the polytoeration catalysts by adding chelating reagents to deactivate and precipitate the catalyst to the molten polymer and subsequently

filtration or adsorption to remove the transformed catalyst components. Although these processes were time and energy intensive, the resulting purified polymers could be stabilized much more easily with conventional antioxidants to remove harmful impurities, particularly catalyst residues. Due to the high demand for both polyethylene and polypropylene, the cost of removing such residues could be accounted for prices of final products.

At present, in many cases the catalyst residues are deactivated and removed only to a small extent or not at all and left in the polymer. This means increased demands on any stabilizers used in such polymers containing catalyst residues to achieve adequate and satisfactory stabilization efficiency.

U.S. Pat. No. 5,488,079, it is disclosed that polyolefin compositions produced in the presence of Ziegler or metallocene-type catalysts in which the catalyst has not been removed from the polyolefin can be stabilized by the addition of a substituted phosphine such as tris (2,4-di-tert-butylphenyl) phosphine.

U.S. Pat. No. 5,238,979 and European Patent Application 393,030 disclose the use of cyclic monophosphites in polyolefin resins containing Ziegler-type complex catalyst residues. The present invention describes the use of trialkanolamine triphosphites which are structurally very different from the prior art compounds used in U.S. Pat. 5,238,979.

Trialkanolamine triphosphites suitable for stabilizing polyolefins are described in U.S. Pat. 5,276,076, 5,326,802, 5,331,031, 5,334,739, 5,344,860, 5,373,040, 5,405,893,

489,635 or 5,489,636.

SUMMARY OF THE INVENTION

The invention relates to polyolefin compositions comprising catalyst residues and which are stabilized against oxidative, thermal and / or light-induced degradation with an effective stabilizing amount of trialkanolamine triphosphite

More particularly, the invention relates to a composition comprising

(a) an oxidative, thermal and / or light-induced degradation polyolefin containing at least one residue of a transition metal or a main group metal or a mixture thereof in an amount of 10 to 1000 ppm due to the use of the metal as a catalyst or co-catalyst to effect polymerization of said polyolefin; and

(b) an effective stabilizing amount of a compound of formula (I)

where n is 0 or 1 if n is 0,

Q represents a direct bond, or

when n is 1, Q represents a sulfur atom or a group

-CR ^X R ² -, wherein R ¹ and R ² are each independently hydrogen, straight or branched (C 1 -C 18) alkyl, phenyl, tolyl or anisyl, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^s , Y ®, Z ^x , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ^{6 are} each independently hydrogen, straight or branched (C 1 -C 18) alkyl, bicycloalkyl (C až-C 10) group, phenyl, benzyl, 1-phenylethyl, cyclohexyl, 1-methylcyclohexyl, cyano, halogen, nitro, trifluoromethyl, hydroxy, amino, (C až-C alk) alkanoyl group , (C 1 -C 18) alkoxy or E ^x E ² E ³ Si, wherein E ¹ , E ² and E ³ are each independently hydrogen, C 1 -C 4 alkyl, or

The phenyl group I and the symbols A ¹ , A ² and A ³ each independently represent a straight or branched alkylene group having 1 to 18 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms or a branched alkylene group having 1 to 8 carbon atoms chiral center.

If any of the radicals R ¹ , R ² , Y ¹ to Y ®, Z ^x to Z ® and A ^x to A ³ represents a straight or branched alkyl group having from 1 to 18 carbon atoms, these are alkyl groups.

us, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, 2-ethylhexyl, n-octyl, tert.octyl, lauryl, n-octadecyl, eicosyl and triacontyl groups; when any of these radicals represents a bicycloalkyl group having 7 to 10 carbon atoms, it is, for example, isobornyl or adamantyl; when any of these radicals is a halogen atom, it is, for example, a fluorine, chlorine or bromine atom; when any of these radicals represents an alkanoyl group having 2 to 18 carbon atoms, it is, for example, acetyl, propionyl, butyryl or decanoyl; when any of these radicals is an alkoxy group having 1 to 18 carbon atoms, it is, for example, methoxy, ethoxy, propoxy, n-butoxy, n-pentoxy, hexyloxy, heptyloxy or decyloxy.

When any one of A ^x to A ³ represents a C 5 -C 6 cycloalkylene group, it is, for example,

1,2-cyclopentyl, 1,3-cyclopentyl, 1,2-cyclohexyl,

A 1,3-cyclohexyl or 1,4-cyclohexyl group; when any of these symbols represents a straight or branched alkylene group having 1 to 18 carbon atoms, it is, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene or dodecylene.

Preferred are compositions wherein in component (b) n is 0 or 1, when n is 0, Q is a direct bond, or when n is 1, Q is a methylene or ethylidene group, Y ^x , Y ² , Y ³ , Y *, Y ^s , Y ®, Z ^x , Z ² , Z ³ , Z ⁴ , Z ^s and Z ® each represent a tert-butyl group, and the symbols A ^x , A ³ and A ³ each represent an ethylene group or a 2-propylene group, wherein the secondary carbon atom is attached to the oxygen atom.

Of particular interest is a composition in which in component (b)

n is 0,

Q represents a direct bond, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^s , Y ⁶ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ^s and Z ⁶ are tert-butyl, and A ^x , A ² and A ³ are each an ethylene group.

Ziegler-type complex supported catalysts, which are a halogen-containing magnesium compound, can yield polymer yields (for a given amount of transition metal, e.g., titanium, which is the major component of the catalyst), ranging from hundreds to thousands of those obtained using a non-catalyst. is supported on a support (such a catalyst system comprises diethylaluminum monochloride and an activated mixture of titanium tetrachloride and aluminum chloride prepared by reducing titanium tetrachloride with metallic aluminum and grinding the reaction product). Such catalyst systems leave catalyst residues that are removed from the resulting polyolefin resin as described above. Although such supported catalysts provide higher polymer yields for a given amount of transition metal, which is the major component of the catalyst, the concentration of transition metal bound to the support is low. The amount of transition metal component bound to the support is less than 1% to 10% by weight. a solid catalyst component. The polymer yield per unit weight of supported catalyst is from several thousand to tens of thousands of units.

As mentioned above, the support and catalyst residues remaining in the resin may adversely affect the stability of the polyolefin resins. Magnesium, aluminum and other auxiliary catalytic8

Thus, compounds still present in the polymer due to the presence of catalyst residues may deteriorate thermal stability, odor, color, corrosion resistance, weathering stability, and other physical properties of any shaped polymeric products. In particular, the problem of poor weathering stability is serious, since large quantities of these molded polyolefin resin products are used outdoors.

The amounts of catalyst residues present in the polyolefin are from 10 to 1000 ppm, preferably from 10 to 500 ppm, and most preferably from 10 to 100 ppm.

Preferred compositions of the invention include component (a) wherein the catalyst residues comprise aluminum, boron titanium, zirconium, chromium, vanadium, or mixtures thereof. Aluminum residues are particularly important in the context of the invention.

In general, polyolefins that can be stabilized include:

Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example cyclopentene or norbornene, further polyethylene (optionally crosslinked), for example high density polyethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density polyethylene very high molecular weight (HDPE — UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LDPE), linear branched low density polyethylene (BLDPE).

2. Mixtures of the polymers referred to in paragraph 1, for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as copolymers of ethylene and propylene, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), copolymers of propylene and 1-butene, copolymers and 1-buterium, ethylene and hexene copolymers, ethylene and methylpentene copolymers, ethylene and heptene copolymers, ethylene and octene copolymers, propylene and butadiene copolymers, isobutylene and isoprene copolymers, ethylene and alkyl acrylate copolymers, ethylene and alkyl acrylate copolymers, their copolymers with carbon monoxide or copolymers of ethylene and acrylic acid and their salts (ionomers), as well as terpolymers of ethylene with propylene and diene, such as hexadiene, dicyclopentadiene or ethylidene-norbornene, and mixtures of these copolymers with each other and with the polymers mentioned above referred to in paragraph avci 1, for example copolymers of polypropylene and ethylene with propylene, copolymers of LDPE and ethylene with vinyl acetate (EVA), copolymers of LDPE and ethylene with acrylic acid (EAA), copolymers of LLDPE and ethylene with vinyl acetate, copolymers LLDPE and ethylene with acrylic acid and ethylene copolymers of polyalkylene and carbon monoxide and mixtures thereof with other polymers, for example polyamides.

A preferred polyolefin polymer according to the invention is a homopolymer or copolymer of propylene or ethylene, in particular the polyolefin is polypropylene or polyethylene.

Also particularly preferred is a composition comprising as component (a) a polyolefin which has not been subjected to solids removal or a similar process which reduces the content of catalyst residues.

The compounds of formula I are preferably added to the component (a) to be stabilized in an amount of 0.01 to 5%, typically 0.05 to 3%, more preferably 0.05 to 1%, based on the weight of component (a) .

In addition to the compounds of formula I, the novel compositions may contain other auxiliary additives (auxiliary stabilizers, co-stabilizers), such as the following typically:

1. Antioxidants

1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol,

2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6 - (1'-methyl-1'-undecyl) phenol, 2,4-dimethyl-6- (1'-methyl-1'-heptadecyl) phenol, 2,4-dimethyl-6- (1'-methyl-1'-tridecyl) ) phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkylated hydroquinones, for example

2,6-di-tert. butyl-4-methoxyphenol, 2,5-di-tert. hydroquinone,

2.5- diterc. amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,

2.6- diterc. butylhydroquinone, 2,5-di-tert-butyl-4-hydroxy or 1,

3,5-di-tert. butyl-4-hydroxyanisole, 3,5-di-tert. butyl 4-hydroxyphenyl stearate, bis (3,5-di-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols such as α-tocopherol, β-tocopherol, gamma-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 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, for example 2,2'-methylenebis (6-tert.

-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2 ' -methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2 'methylenebis (4,6-di-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'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl) butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) - 4-methylphenol), 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis- (5-tert-butyl-4-hydroxy-2- methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol-bis- [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) enyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzy) l) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl); butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 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'-tetraterc. butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2) 6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert. butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecylmercaptoethyl-2 , 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl) 4-hydroxybenzylJmalonát.

1.9. Aromatic hydroxybenzyl compounds, for example

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 such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis 5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-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, for example 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, calcium salt of 3,5-di-monoethyl ester. butyl-4-hydroxybenzylphosphonic acid.

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

13.1. Esters of B- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monovalent or polyhydric alcohols, for example with methanol, ethanol, 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, trimethyl-4-methanediol, 4-thiapentadecanol -2,6,7-trioxabicyclo [2.2.2] octane.

14.1. Β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid esters with monovalent or polyhydric alcohols such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioethane, 3-thentadiene, 3-thioethane trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

15.1. B- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid esters with monovalent or polyhydric alcohols, for example with 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, 2,6-trimethylhexanol, trimethylhexanethane 7-trioxabicyclo [2.2.2] octane.

16.1. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monovalent or polyhydric alcohols, for example with 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, trimethylhexanediol, trimethylhexanediol, trimethylhexanediolop, 1 , 7-trioxabicyclo [2.2.2] octane.

17.1. Β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amides, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5'-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

18.1. Ascorbic acid (vitamin C).

19.1. Amine-based antioxidants such as 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'-di (naphthyl-2) -p-phenylenedianine, Nizopropyl-N'-phenyl-phenylenediamine, N- (1,3-dimethylbutyl) -N 'phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) -diphenylamine, N, N 1'-dimethyl-N, N'-di-sec-butyl-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di- (4-phenyl) amine, 2,6-di-tert butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di - [(2- methylphenyl) amino] ethane, 1,2-di- (phenylamino) propane, (o-tolyl) -biganide, di- [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tertioctylated N-phenyl 1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenylamine, a mixture of mono- and dialkylated nonyldiphenylamine, a mixture of mono- and di-alkylated dodecyldiphenylamine, a mixture of mono- and dialkylated isopropyl / isohexyldiphenylamine, a mixture of mono- and dialkylated tert. butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert.octylphenothiazine, a mixture of mono- and dialkylated tert.octylphenothiazine, N-allylphenothiazine, N, N, N ', N'-Tetrafenyl-1,4-diamino-2-butene, N, N-bis- (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine, bis- (2 2,6,6-tetramethylpiperidin-4-yl) sebalate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. DV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) benztriazoles, 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-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5) 'tert-butyl-2' hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'octyloxyphenyl) benzotriazole,

2- (3 ', 5'-diterc.amyl-2'-hydroxy-benzotriazole,

2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl ) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole,

2- (3'-tert-butyl-3'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' (2-methoxycarbonylethyl) phenyl) bezotriazole, 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 and 2- (3'-tert-butyl-2'-hydroxy-5) 1- (2-isooctyloxycarbonylethyl) phenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol], transesterification product 2- [3 ' tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole by polyethylene glycol 300, a compound of formula [R-CH _and CH ₂ -COO (CH ₂ )], wherein R is 3'-tert. butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl group.

2.2 2-hydroxybenzophenones, e.g. 4-hydroxy-, 4-methoxy, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy- 4,4'-dimethoxy derivatives of 2-hydroxybenzophenone.

2.3 Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl-resorcinol, bis (4-tert-butylbezoyl) resorcinol, benzoyl-resorcinol, 2,4-di-tert-butylphenyl ester - di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester,

3,5-Di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl ester.

2.4 Acrylates, for example, ethyl .alpha.-cyano-6, .beta.-diphenyl acrylate, isooctyl .alpha.-cyano-.beta. -cyano-B-methyl-p-methoxycinamate, methyl-α-methoxycarbonyl-p-methoxycinamate, and N- (B-methoxycarbonyl-β-cyanvinyl) -2-methylindoline.

2.5. Nickel compounds, for example, nickel complexes with 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol] such as a 1: 1 or 1: 2 complex, optionally with other ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts with 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, for example methyl or ethyl ester thereof, nickel complexes with ketoximes, for example 4- methylphenyl-undecylketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with other ligands.

2.6 Sterically hindered amines, e.g. bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, bis (1,2,2,6,6-pentamethylpiperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation product 1-hydroxyethyl) -2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid, the condensation product 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, condensation product N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and

4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3 5-triazine α1,2-bis (3-aminopropylamino) ethane, condensation product 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- penta-methyl-4-piperidyl) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N, N'-bis (• 2,2, 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product 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 Registry [136504-96-6]), N- (2,2,6,6-tetramethyl) -4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentam ethyl-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.

2.7. Oxamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyqanilide, 2,2'octyloxy-5,5'-di-tert-butxanilide, 2,2'-didodecyloxy-5,5'-di-tert. butoxanilide, 2-ethoxy-2'-ethoxanilide,

N, N'bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-etoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, ortho mixtures and para-methoxy-disubstituted oxanilides and mixtures of ortho- and para-ethoxy-disubstituted oxanilides.

2.8 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) enyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine,

2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6 -bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 - (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (218

-hydroxy-3-butyloxypropyloxy-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-dimethyl) -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-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4, 6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- ( 2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine.

3. Metal deactivators, for example Ν, Ν'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4- hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl-bisphenylhydrazide, Ν, Ν'-diacetyladipoyl dihydrazide, N, N'bis oxalyl dihydrazide, N, N'bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl-alkyl phosphites, phenyl-dialkyl-phosphites, tris (nonylphenyl) phosphite, trilauryl-phosphite, trioctadecyl-phosphite, distearyl-pentaerythritol-diphosphite, tris (2,4-diterc) butylphenyl) phosphite, diisodecyl-pentaerythritol diphosphite, bis- (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol-diphosphite, bis (2,4,6-triter-butylphenyl) pentaerythritol-diphosphite, tristearyl-sorbitol-trifunctional, tetrakis (2, 4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetraterc. butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetraterc. butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphine, bis (2,4-di-tert-butyl) 6-methylphenyl) ethyl phosphite.

5. Hydroxylamines, for example N, N-dibenzylhydroxylamine,

N, N-diethylhydroxylamine, Ν, Ν-dioctylhydroxylamine, N, N-di19-laurylhydroxylamine, Ν, Ν-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, Ν, Ν-dioctadecylhydroxylamine, N, N-dihexadecylhydroxylamine, N -octadecylhydroxylamine, Ν, Ν-dialkylhydroxylamines derived from hydrogenated tallow amines.

6. Nitrons such as N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N-hexadecyl-α -pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-aheptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, di-nitadecylnitrone, odinitrile, nitro-Ν-hexadecylnitrone, of amine hydrogenated tallow.

7. Thio-containing synergistic additives, for example dilauryl thiodipropionate or distearyl thiodipropionate.

Peroxide-disrupting compounds, for example β-thiodipropionic acid esters, for example, its lauryl ester, stearyl ester, myristyl ester or tridecyl ester, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl β-disodecyl p-disodecyl p-disodecyl p-disodecyl p-disodecyl p-disodecylpentisol).

9. Basic co-stabilizers, for example melamine, polyvinyl pyrrolidone, dicyandiamide, trialyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate , magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.

10. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulphates of preferably alkaline earth metals, organic compounds such as mono- or polycarboxylic acids or salts thereof, for example 4-tert. butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, polymeric compounds such as copolymers containing ions (ionomers).

11. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black and graphite, sawdust or fibers of other natural products, synthetic fibers.

12. Other additives, for example, plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, fluorescent whitening agents, flame retardants, antistatic agents and blowing agents.

13. Benzofuran-2-ones and indolinones, for example as described in US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052 A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or 3- [4] - (2-acetoxyethoxy) phenyl] -5,7-di-tert. butylbenzofuran-2-one,

5,7-di-tert. butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di terc. 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. butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert. butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert. benzofuran-2-one.

Auxiliary ^- Stabilizers, other than benzofuran-2-ones mentioned under 13, are added typically in concentrations of 0.01 to 10%, of the total weight of the material to be stabilized.

Other preferred compositions contain, in addition to components (a) and (b), other additives, preferably phenolic antioxidants, light stabilizers and / or processing stabilizers.

Preferred additives are in particular phenolic antioxidants (list item 1), sterically hindered amines (list item 2.6) and peroxide-destroying compounds (list item 8).

Particularly interesting phenolic antioxidants are selected from the group consisting of n-octadecyl-3,5-di-tert-butyl-4-hydroxy-hydrocinamate, neopentantetrayl-tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinamate), di-n-octadecyl- 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxapctamethylene-bis (3-methyl-5-tert-butyl-4) hydroxyhydrochlorinate), 2,6-di-tert. butyl-p-cresol, 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1, 1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinamoyloxy) ethyl] isocyanurate, 3,5-di (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl-4- hydroxyanilino) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis (ethyl-3,5-di-tert-butyl- 4-hydroxybenzylphosphonate), ethylene-bis [3,3-di (3-tert-butyl-4-hydroxyphenyl) butyrate], octyl-3,5-di-tert. butyl 4-hydroxybenzyl mercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocinamoyl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhydrocinamoyloxy) ethyl] oxamide.

Most preferred phenolic antioxidants are neopentantetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl-3,5-di-tert. butyl 1-4-hydroxy oxycinamate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene,

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidenebis (4,6-di-tert-butylphenol) .

The tri-alkanolamine triphosphites of formula (I) forming component (b) protect the phenolic antioxidants used in polyolefins containing catalyst residues, especially aluminum residues, from discoloration and provide excellent color of the polyolefin resin.

Particularly interesting hindered amines are selected from the group consisting of bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di (1). , 2,2,6,6-pentamethylpiperidin-4-yl) - (3,5-di-tert-butyl-4-hydroxybenzyl) butyl malonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2 , 6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, tris (2,2,6 6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxo-piperazin-4-yl) ethane, 2,2,4,4-tetramethyl-7 -oxa-3,20-diaza-21-oxodispiro [5,1,11,2] heneicosane, a polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino -2,2,6,6-tetramethylpiperidine), a polycondensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, a polycondensation product of 4,4'-hexamethylenebis (amino- 2,2,6,6-tetramethylenepiperidine) and 1,2-dibromethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3 4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxylate, a polycondensation product of 2,4-dichloro-6-morpholino-s-triazine, and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N' N-tetrakis [(4,6-bis (butyl-2,2,6,6-tetramethylpiperidine) -4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl] f, B ', B'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6] , 6-tetramethylpiperidin-4-yl / B, B, B ', B' tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) diethyl] -1,2,3 , 4-butanetetracarboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidine-4-carboxylate), 4,4'-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one) and bis (1- octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

The most preferred hindered amines are bis (2,2 ₇ 6,6 tetra23-methylpiperidin-4-yl) sebacate, the polycondensation product of l- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid j , a polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N'-N, N - tetrakis [(4,6-bis (butyl- (2,2,6,6-tetramethylpiperidin-4-yl) amino) -s-triazine-2-yl] -1,10-diamimo-4,7-diazadecane, or bis- (1-octyloxy-2,2,6,6-tetraethylpiperidin-4-yl) sebacate.

* Also preferred additional additives (stabilizers) are benzofuran-2-ones, such as those described, inter alia, in US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A- 5,216,052, US-A-5,252,643, DE-A-4,316,611, DE-A-4,316,622, DE-A-4,316,876, EP-A-0 589 839 and EP-A-0 591 102nd

Examples of such benzofuran-2-ones include compounds of formula

in which

R ¹¹ represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system,

R ^{, xa} represents a hydrogen atom,

R 1 ^{, X 4} is hydrogen, C 1 -C 12 alkyl, cyclopentyl, cyclohexyl or chloro,

R ^'13 is as defined as R' ¹² or R ^{, X 4} , or is a radical of formula.

O • I 16 - _(CH2 ^ C ~ -OR ^{1 b,}

or -D-E, wherein

R ' ^X6 is hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 18 carbon atoms interrupted by oxygen or sulfur, a dialkylaminoalkyl group having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl substituted by one to three alkyl radicals together having at most 18 carbon atoms, p is 0, 1 or 2 substituents R ^3-7 independently of one another are hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, , phenyl, phenyl substituted with one or two alkyl radicals containing together - not more than 16 carbon atoms, the remainder of the formula -CH OH, -CH -OCH, * 2 ', 2'-t2-tc-tl

O or -C ^H ^ -OC-R ^'20 , or together with the nitrogen atom to which they are attached, form a piperidine or morpholine moiety, t is 1 to 18,

R ^'20 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms,

A represents a C 2 -C 22 alkylene group which may be interrupted by nitrogen, oxygen or sulfur,

R @ ¹³ represents a hydrogen atom, a C1 -C18 alkyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a phenyl group substituted by one or two alkyl radicals containing up to 16 carbon atoms together or a benzyl group,

R ^'13 represents an alkyl group having 1 to 18 carbon atoms,

D represents an oxygen atom, a sulfur atom, a -SO-, -SO or -C (R ^'21 ) ₂ - group, the substituents R' ^21, independently of one another, represent a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, both residues R ^'21 together contain 1 to 16 carbon atoms, or R' ^{21 is} furthermore a phenyl group or a radical of formula

where the symbols s, R ' ^xe and R' ^{17 are} as defined above,

E is a radical of formula

wherein R ^'11 , R' ¹² and R ^{'14 are} as defined above, and

R ^'15 represents a hydrogen atom, a C 1 -C 20 alkyl group, a cyclopentyl group, a cyclohexyl group, a chlorine atom or a radical of the formula -CH 2 -C -OR' ¹ ® or -CH 2 -CN (R ' ^{X 7} ) 2, where they have symbols

R ' ^x ® and R ^{, X 7} as defined above, or R' ^{x 5} and R ^'14 together form a tetramethylene residue.

Also preferred are benzofuran-2-ones wherein R 1 ^{, X 3} is hydrogen, C 1 -C 12 alkyl, cyclopentyl, cyclohexyl, chlorine, or a radical of formula

or -DE, wherein the symbols, s, R ^{, x} ®, R ^'17 , D and E are as defined above, and R ^{, x} ® is preferably hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl .

Also preferred are those benzofuran-2-ones in which R ^'11 represents a phenyl group or a phenyl group substituted by one or two alkyl radicals containing up to 12 carbon atoms together, R' ¹² represents a hydrogen atom, R ' ^{X 4} represents a hydrogen atom or an alkyl group C 1 -C 12, R ^'13 is hydrogen, C 1 -C 12 alkyl,

0 II ₁₆ II ₁₇ - (C ^ CHjy -OR ^15th HCH -NCR ^ '^ ¹ or -DE, R ¹⁵ is H, alkyl having 1 to 20 carbon atoms, ⁰

II un _ or R ' ^xs and symbols s, beginning.

-CH ₂ -C-OR ^{, IU} or -CH 2 -CN (R ¹⁷ ) 2

R ^'14 together form a tetramethylene residue, where R ^{, xe} , R' ¹⁷ , D and E have the meanings defined for

Of particular interest are also those benzofuran-2-ones in which R ^'13 represents a hydrogen atom, a C 1 -C 12 alkyl group or a -DE group, R * ¹² and R' ¹⁴ independently of one another are hydrogen or alkyl. C1-C4, and R ' ^x is C1-C20alkyl, wherein D and E are as defined above.

Interest are finally also those benzofuran-in particular 2-ones in which R ¹³ is alkyl of 1 to 4 carbon atoms or -DE; R ', ^{X 2} and R ^{X 4} are all H, and ^{R, x s} is C C 1 -C 4, cyclopentyl or cyclohexyl, wherein D is -C (R ^{, 2X} ) _and - and E is a radical of formula

wherein the substituents R ^'21 are identical or different and are each alkyl of 1 to 4 carbon atoms and the symbols R ^11, R ^X2, R ^14, and ^{R, x s} are as defined above.

The amounts of benzofuran-2-ones used as additives may vary within wide limits. The novel compositions may typically contain them in amounts of 0.0005 to 10% by weight, preferably 0.001 to 5% by weight, most preferably 0.01 to 2% by weight.

A preferred embodiment of the invention is the use of a compound of formula I for stabilizing a polyolefin containing at least one of a transition metal or a main group metal or a mixture thereof in an amount of 10 to 1000 ppm as a result of using the metal as a catalyst or co-catalyst to polymerize said polyolefin against oxidative, thermal and / or light-induced degradation.

The invention also relates to a process for stabilizing a polyolefin comprising at least one residue of a transition metal or a main group metal or mixture thereof in an amount of 10 to 1000 ppm due to the use of the metal as a catalyst or co-catalyst to effect polymerization of said polyolefin against oxidative, thermal and / and light-induced degradation, and the method comprises incorporating a compound of formula I as component (b) into the material or applying a compound of formula I as component (b) to the material.

The following examples illustrate the invention in more detail. The amounts and percentages given are amounts and percentages by weight.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Polypropylene stabilization

The general procedure below is used to prepare various polypropylene formulations in which additives are mixed into the polymer.

To 1000 g of Himont Profax 6501 powder polypropylene (obtained by bulk phase polymerization) were added various test additives at the concentration given in the various examples and in the tables below. The phenolic antioxidant concentration is adjusted to 750 ppm. An acid scavenger, calcium stearate, is also used at a concentration of 750 ppm. The triethylaluminium concentration ranges from 0 to 500 ppm, corresponding to 0 to about 112 ppm of aluminum in the final formulation.

The resulting powder is further stirred for 20 minutes in a drum mixer. The blended mixture is then processed by the melt process using a Superior MPM 2.54 cm extruder equipped with a screw for mixing polyolefins with a Maddock mixing portion in the measuring zone of the screw. The outlet temperature is set at 274 ° C. The extruded melt strip is rapidly cooled in a water bath and pelletized using a Conair strand cutter. A sample of 100 g pellets from this first extrusion is retained for further testing and the remainder of the extrudate is passed through the extruder again. In this way, the pellet residues are removed after the third and fifth extrusions.

Polypropylene pellets are tested for melt flow rate by the ASTM 1238-90 method using an extrusion plastometer (Tinius-Olsen) with a 2.16 kg cartridge at 230 ° C. The yellowing index is measured by the ASTM 1925-90 method on an Applied spectrophotometer. Color Systems Spectrophotometer with large viewing slot, including spectral component, light source C, at 2 ° viewing angle on 3.175 mm thick pressed plates.

Polymer: Himont Profax 6501 polypropylene, Ti / Al catalyst; the Spheripol procedure; nominal melt index = 5.3 dg / min at 2.16 kg and 230 ° C.

Extrusion conditions: Zone 1 at 246 ° C, Zone 2 at 260 ° C, Zone 3 at 274 ° C, Zone 4 at 274 ° C; extruded with non-closed hopper; 90 rpm; holding time in the cylinder approximately 1 minute.

Extruder: Superior MPM 2.54 cm; 241 1 / d.

Sieve Properties: 20-60-100-60-20.

Type of screw: screw for polyolefins with Maddock mixing head.

Pressing: 232 ° C, 3 minutes low pressure, 3 minutes high pressure, minutes cooling.

Example 1 illustrates the prevention of coloration from the first to the fifth pass of a polypropylene composition containing 750 ppm neopentantetrayl tetrakis (3,5-di-tert-butyl-4-hydroxycinamate), Irganox 1010 (Ciba Specialty Chemicals), 0 to 750 ppm of a compound of Formula I where n is 0,

Q is a direct bond, A ^x to A ³ are each an ethylene group, and Y ^x to Y ® and Z ^x to Z ® each are tert-butyl, Irgafos 12 (Ciba Specialty Chemicals) and different amounts of aluminum to achieve different concentrations of residual aluminum of formula I is determined by determining the values of Y1) below in the composition. The ability of a compound of the invention to prevent the color change from the Yellowness Index (Table 1) for each residual aluminum concentration in the composition. Lower yellows mean less color change.

index values

Table 1

concentration of the compound of the general formula ca I (ppm) triethylaluminium yellowing index ppm ppm as Al after the first pass through the extruder after the fifth transition extruder 0 0 0 7.45 8.85 750 0 0 6.62 8.17 0 10 2 7.74 9.54 750 10 2 6.64 8.04 0 50 12 7.48 10.11 750 50 12 6.85 7.90 0 100 24 7.35 9.62 750 100 24 7.01 8.21 0 500 118 7.47 10.44 750 500 118 7.04 8.51

Irgafos 12 (Ciba Specialty Chemicals) is a compound of formula Ia

Example 2

Polypropylene stabilization

When 750 ppm of Irganox 1010 in the composition of Example 1 is replaced with 750 ppm of N, N ', N'-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, Irganox 3114 (Ciba Specialty Chemicals) is observed. the same stabilizing effect of Irgafos 12 (Ciba Specialty Chemicals, compound of formula I, see Example 1) in preventing discolouration in the case of polypropylene containing different concentrations of aluminum residues, as shown in Table 2 below.

Table 2

concentration of the compound of the general formula ca I (ppm) triethylaluminium yellowing index ppm ppm as Al after the first pass through the extruder after the fifth transition extruder 0 0 0 7.98 9.98 750 0 0 7.54 7.96 0 10 2 8.06 10.48 750 10 2 8.15 9.53 ABOUT 50 12 7.73 10.55 750 50 12 8.45 8.81 0 100 24 8.41 10.36 750 100 24 8.27 8.66

From the data given in Examples 1 and 2, it is clear that the addition of trialkanolamine triphosphite protects the polyolefin from discoloration even if a substantial amount of the metal catalyst or cosolvent catalyst is present.

Example 3

This example illustrates the ability of compounds of formula I, such as Irgafos 12 (Ciba Specialty Chemicals, see Example 1) to complex with trialkylaluminum. All trialkylaluminium operations are carried out in a dry vessel under argon atmosphere with a carefully maintained air inlet.

To a solution of 2 g (1.37 mmol) of Irgafos 12 in 4 mL of chloroform was added 1.37 mL (1.37 mmol) of a 1M solution of triethylaluminum in hexane. ^{The 3X} P { ^X H} NMR spectrum shows resonances at δ 132.8 ppm and 32.7 ppm, while Irgafos 12, which is not complexed, exhibits a single resonance (singlet) at δ 137.1 ppm.

Example 4

This example demonstrates that not all phosphites form complexes with trialkylaluminum.

The procedure of Example 3 was repeated with 0.88 g (1.37 mmol) of tris- (2,4-di-tert-butylphenyl) phosphite, Irgafox 168 (Giba Specialty Chemicals), 1.37 mL (1.37 mmol) of the IM solution. triethylaluminium in hexane and 4 ml of chloroform. NMR showed no complex formation.

Claims (13)

PATENT CLAIMS What is claimed is: 1. A composition comprising (a) an oxidative, thermal and / or light-induced degradation polyolefin containing at least one of a transition metal or a main group metal or a mixture thereof in an amount of 10 to 1000 ppm as a result of using the metal as a catalyst or auxiliary catalyst to effect polymerization of said polyolefin; and b) an effective stabilizing amount of a compound of formula I wherein n is 0 or 1, when n is 0, Q is a direct bond, or when a is 1, Q is a sulfur atom or a group -CR 1 R ³ - wherein R ¹ and R ² are each independently hydrogen, straight or branched (C 1 -C 18) alkyl, phenyl, tolyl or anisyl, Y ¹ , Y ² , Y ^3, Y ^4, Y ^a, Y ^6, Z ^1, Z ^2, Z ^3, Z ^4, Z ^a and Z ^6, independently of one another are hydrogen, straight or branched alkyl having 1 to 18 carbon atoms, a bicycloalkyl (C až-C 10) group, phenyl, benzyl, 1-phenylethyl, cyclohexyl, 1-methylcyclohexyl, cyano, halogen, nitro, trifluoromethyl, hydroxy, amino, (C až-C až) alkanoyl, (C 1 -C 18) alkoxy or E ¹ E ² E ³ Si, wherein E ¹ , E ² and E ³ are each independently hydrogen, C 1 -C 4 alkyl or phenyl, and A ^1, a ² and a ³ before dependently of one another are linear or branched alkylene group having 1 to 18 carbon atoms, cycloalkylene of 5 to 6 carbon atoms or branched alkylene radical -C 8 alkyl with the chiral center. A composition according to claim 1, characterized in that it comprises, as component (b), a trialkanolamine triphosphite of the general formula I, in which n is 0 or 1, when n is 0, Q represents a direct bond or if q has a value 1, Q represents a methylene or ethylidene group, the symbols Y ¹ , Y ² , Y ³ , Y ⁴ , Y ^s , Y ⁶ , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ^s and Z ⁶ respectively represent tert-butyl group, and where a ^x, a ² and a ³ are each ethylene or 2-propylene radical wherein the secondary carbon atom is bonded to an oxygen atom. Composition according to Claim 1, characterized in that it comprises, as component (b), a trialkanolamine triphosphite of the general formula I, in which n has the value 0 _r Q is a direct bond, Y ^x , Y ² , Y ³ , Y ⁴ , Y ^s , Y ^e , Z ^x , Z ² , Z ³ , Z ⁴ , Z ⁵ and Z ⁶ are tert-butyl, and A ^x , A ² and A ³ are each an ethylene group. The composition of claim 1, wherein the catalyst residue comprises aluminum, boron, titanium, zirconium, chromium vanadium, or mixtures thereof. The composition of claim 1, wherein the remainder of the catalyst comprises aluminum. The composition of claim 1, wherein the polyolefin is a homopolymer or a copolymer of propylene or ethylene. The composition of claim 1, wherein the polyolefin is polypropylene or polyethylene. The composition of claim 1, wherein the polyolefin has not undergone particulate removal or the like to reduce the content of catalyst residue. Composition according to claim 1, characterized in that it contains component (b) in an amount of 0.01 to 5%, based on the weight of component (a). The composition of claim 1, further comprising a phenolic antioxidant, a light stabilizer, and / or a processing stabilizer. The composition of claim 1, further comprising at least one benzofuran-2-one compound as an auxiliary additive. and A process for stabilizing a polyolefin comprising at least one residue of a transition metal or a main group metal or mixture thereof in an amount of 10 to 1000 ppm as a result of using the metal as a catalyst or co-catalyst to effect polymerization of said polyolefin against oxidative, thermal and / or light induced degradation, characterized in that a trialkanolamine triphosphite of formula (I) according to component (b) according to claim 1 is incorporated into or applied to the polyolefin. Use of a trialkanolamine triphosphite of the general formula I according to component (b) according to claim 1 for stabilizing a polyolefin which contains at least one residue of a transition metal or a main group metal or a mixture thereof in an amount of 10 to 1000 ppm. a catalyst for effecting polymerization of said polyolefin against oxidative, thermal and / or light-induced degradation.