CA2236638A1 - Vitamin e formulations for stabilising polymeric organic materials - Google Patents

Vitamin e formulations for stabilising polymeric organic materials Download PDF

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CA2236638A1
CA2236638A1 CA002236638A CA2236638A CA2236638A1 CA 2236638 A1 CA2236638 A1 CA 2236638A1 CA 002236638 A CA002236638 A CA 002236638A CA 2236638 A CA2236638 A CA 2236638A CA 2236638 A1 CA2236638 A1 CA 2236638A1
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tert
butyl
bis
composition according
acid
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Rita Pitteloud
Christoph Krohnke
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention relates to a composition, which comprises A) an organic polymeric material and B) a stabiliser mixture consisting b1) of .alpha.-tocopherol, b2) of a solid polyhydroxy compound selected from the group consisting of triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol, or b3) of an acid-binding material or of a mixture consisting of components b2) and b3). This invention also relates to the stabiliser mixture B) as well as to its use for stabilising polymeric materials, in particular food wrappings.

Description

CA 02236638 1998-0~-01 Vitamin E formulations for stabilisinq polymeric orqanic materials The present invention relates to a composition, which comprises A) a polymeric material, B) a stabiliser mixture consisting of a-tocopherol, of a solid polyhydroxy compound and/or of an acid-binding compound. This invention also relates to the stabiliser mixture as such as well as to its use for stabilising polymers, in particular food wrappings.

The stabilisation of polymers such as polyethylene or polypropylene with vitamin E (a-toco-pherol) has been known for a long time and is described, inter alia, in WO 90/07547. One disadvantage of this stabiliser is the discoloration which takes places at elevated tempera-tures.

The reduction of this discoloration, in particular of the yellowing during the processing steps, by means of a-tocopherol is described with a number of polyhydroxy compounds in WO 93/10175.

The polyhydroxy compounds mentioned there have the disadvantage of being liquid or low-melting compounds which form an oily to sticky paste-like composition together with a-toco-pherol which in turn is an oily material having a melting point of 2.5-3.5~ C.

However, such oils or pastes are not well suitable for incorporation into, for example, poly-mer granules because they stick to the sides of the storage and mixing containers which may cause inhomogeneous distribution during extrusion.

With regard to use aspects, there is thus the need for having a solid stabiliser com position not containing any carriers and which can be added to the polymer and then extruded in simple manner.

This invention provides such stabiliser mixtures which give solid compositions together with organic polymers, which compositions can be processed without leaving oily deposits in the extruder.

The mixture is completely homogeneous and affords polymers which are excellently stabilis-ed against heat. The addition of the selected polyhydroxy compounds results in particularly CA 02236638 1998-0~-01 low yellowing during the thermal processes. Exudation of the polyhydroxy compounds or vo-latilisation owing to low vapour pressure need not be feared when using these compounds.
Because they are completely retained in the polymer, they also unfold their complete effecti-veness.

Compared to the known liquid polyhydroxy compounds, these compounds have better colour behaviour after thermal stress.

The polymers so stabilised are very particularly suitable for food wrappings.

In one of its aspects, this invention relates to a composition, which comprises A) an organic polymeric material and B) a stabiliser mixture consisting b1) of a-tocopherol, b2) of a solid polyhydroxy compound selected from the group consisting of triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol, or b3) of an acid-binding material or of a mixture consisting of components b2) and b3).

The structural formulae of the polyhydroxy compounds are given below.

o~~o~f O--~OH O~O~OH O~O~OH
OH OH OH OH O OH
triglycerol 'il ~.~,;I.J' '~ . )e dipentaerythritol O ~ OH OH
O~O--~O~--OH
OOH OH
1, ;~,u- Ita~l~tl " itul HO-- --OH --OH
HO-- --OH HO----OH HO-- --OH

D-mannitol D-sorbitol xylitol CA 02236638 1998-0~-01 Illustrative examples of polymeric materials are given below.

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-but-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high mole-cular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight poly-ethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe-rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevated temperature).

b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlll of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ~1- or <~-coordinated.
These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, lla and/or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

CA 02236638 1998-0~-01 2. Mixtures of the polymers mentioned under 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, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo-lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene~lsoprene copolymers, ethy-lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alter-nating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylo-nitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo-lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/
styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.

CA 02236638 1998-0~-01 7. Graft copolymers of styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth-acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo-nitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on poly-butadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acry-lonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acry-lates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluaide, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from a"l~-unsaturated acids and derivatives thereof such as polyacry-lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni-triles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu-rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acry-lonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace-tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.

CA 02236638 1998-0~-01 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy-lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybuta-dienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylene-diamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene tereph-thalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.

CA 02236638 1998-0~-01 19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry-lates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenolF, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose buty-rates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, CA 02236638 1998-0~-01 POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The polymeric organic material A) is preferably polyolefin, polystyrene, PVC, polyamide, polyacrylate or polyester. Polyolefin, in particular polyethylene or polypropylene, is parti-cularly preferred.

The solid polyhydroxy compound is preferably ditrimethylolpropane, dipentaerythritol or tri-pentaerythritol.

The polymeric composition can contain an acid-binding material in addition to or instead of the polyhydroxy compound b2).

The acid-binding material is preferably an alkaline earth salt or zinc salt of a C3-C18carboxylic acid, alkaline earth/aluminium carbonate, alkaline earth/aluminium hydroxyborate, alkaline earth/aluminium hydroxyphosphite or zeolite.

Alkaline earth salts or zinc salts of a C3-C1Bcarboxylic acid are particularly preferred. The car-boxylic acid can be saturated or unsaturated, branched or unbranched. It is preferred to use monocarboxylic acids which, however, may be substituted by one or several OH groups.

Typical examples of saturated C3-C18carboxylic acids are propionic acid, butyric acid, valeric acid, capric acid, palmitic acid, stearic acid, lauric acid or lactic acid.

Lactic acid, lauric acid and stearic acid are particularly preferred.

A preferred composition is that, which comprises A) an organic polymeric material and B) a stabiliser mixture consisting bl ) of a-tocopherol and b2) of a solid polyhydroxy compound which is selected from the group consisting of triglycerol, ditrimethylolpropane, dipentaery-thritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol.

Component b1 ) is preferably present in an amount of 0.005 to 2 % by weight, based on the polymer.

CA 02236638 1998-0~-01 Component b2) is preferably present in an amount of 0.005 to 5 % by weight, based on the polymer.

The ratio of b1) to b2) is preferably from 10:1 to 1:10.

Component b3) is preferably present in an amount of 0.005 to 5%, based on the polymer.

Other commercially available additives may also be present in addition to components b1 ) to b3).

1. Antioxidants 1.1. Alkylated monoPhenols. for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dime-thylphenol, 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-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-di-methyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hvdroquinones, for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol, 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. 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-CA 02236638 l998-0~-Ol 2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dimethyl-4-hydroxyphe-nyl) disulfide.

1.5. 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-(a-methylcyclohexyl)-phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-me-thylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl-phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylben-zyl)-4-nonylphenol], 2,2'-methylenebisl6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methyle-nebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopenta-diene, bis~2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha-late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphe-nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane .

1.6. O-, N- and S-benzyl comPounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy-benzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.7. Hydroxybenzylated malonates, for example 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 .

1.8. Aromatic hydroxvbenzyl comPounds, for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxy-benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame-thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

CA 02236638 1998-0~-01 1.9. Triazine comPounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tria-zine, 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-hydroxy-benzyl)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.

1.10. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho-nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-buty~4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

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

1.12. Esters of B-(3.5-di-tert-butvl-4-hvdroxyPhenyl)Propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9--nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy-lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy-droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.13. Esters of ~-(5-tert-butvl-4-hydroxy-3-methylphenyl)Propionic acid with mono- or poly-hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-diol, 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, trimethyl-olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of ~-(3,5-dicyclohexvl-4-hydroxyphenyl)ProPionic acidwith mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, CA 02236638 1998-0~-01 triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6 ,7-trioxabicyclo[2.2.2]octane .

1.15. Esters of 3.5-di-tert-butyl-4-hvdroxyPhenyl acetic acid with mono- or polyhydric alco-hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri-ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2 ,6 ,7-trioxabicyclo[2.2.2]octane.

1.16. Amides of ,~-(3,5-di-tert-butyl-4-hydroxvPhenyl)proPionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl)-hydrazine.

1.17. Ascorbic acid (vitamin C) 1.18. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'bis(2-naph-thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclo-hexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phe-nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-di-methylaminomethylphenol, 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-CA 02236638 1998-0~-01 octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopro-pyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dial-kylated tert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phe-nothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, 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 liqht stabilisers 2.1. 2-(2'-HvdroxyPhenyl)benzotriazoles. for example 2-(2'-hydroxy-5'-methylphenyl)-benzo-triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe-nyl)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'-methyl-phenyl)-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)benzo-triazole, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)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'-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)car-bonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzo-triazole, and 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterifi-cation product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotri-azole with polyethylene glycol 300; [RCH2CH2COO(CH2)3 ~ , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl .

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

CA 02236638 l998-0~-Ol 2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzo-ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben-zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl a-cyano-~,~-diphenylacrylate, isooctyl a-cyano-~,~-diphe-nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-~B-methyl-p-methoxy-cinna-mate, butyl a-cyano-,B-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxy-cinnamate and N-(,B-carbomethoxy-,~-cyanovinyl)-2-methylindoline.

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

2.6. Stericallv hindered amines. for example 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, bis(1,2,2,6,6-pentamethyl-4-pipe-ridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxy-ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate 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-tetramethylpipe-razinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidi-ne, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malo-nate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dion, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate 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, the CA 02236638 l998-0~-Ol condensate of 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-tria-zaspiro[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, 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, 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-dodecylsuccinimid, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8--diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-di~ctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-di-substituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hvdroxyohenyl)-1,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy4-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-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl-phenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hyd-roxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy4-(3-butoxy-2-hyd-roxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1 ,3,5-triazine.

CA 02236638 1998-0~-01 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, 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, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl-oyl)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 phos-phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphos-phite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butyl-phenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butyl-phenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz-[d,g]-1 ,3,2-dioxaphosphocin, 6-fluoro-2,4,8,1 0-tetra-tert-butyl-1 2-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl--6-methylphenyl)ethylphosphite .

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl-hydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-oc-tyl-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-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hepta-decyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxyl-amine derived from hydrogenated tallow amine.

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

CA 02236638 1998-0~-01 8. Peroxide scavenqers, for example esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(,~-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phos-phorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts 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.

11. Nucleatinq agents. for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers").

12. Fillers and reinforcina agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car-bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 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-bu-CA 02236638 1998-0~-01 tyl-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.

A UV absorber or a sterically hindered amine, or both, are preferably additionally present.
Illustrative examples of UV absorbers and sterically hindered amines are indicated above.

This invention also relates to a stabiliser mixture consisting b1 ) of a-tocopherol, b2) of a solid polyhydroxy compound selected from the group consisting of triglycerol, ditrimethylolpro-pane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol, or b3) of an acid-binding material or of a mixture consisting of components b2) and b3).

Components b1 ) to b3) have the meanings and preferred meanings stated above.
The stabiliser mixture can be mixed with apparatus customarily used in the technology, such as mixers, kneaders or the like.

It is also possible to melt the components completely or partially or to dissolve them in a sol-vent and to prepare powders or granules by spraying. Any components which cannot be melted or dissolved can simply be stirred into the melt.

Suitable solvents are ethers, esters, ketones, amides or hydrocarbons.

The stabiliser mixture can be mixed with the polymer e.g. by incorporating the compounds and further optional additives by the standard technological methods. Incorporation can be carried out before or during moulding. The components can be added together or in any sequence.
The components can also be added to the plastic materials to be stabilised in the form of a masterbatch which comprises them, for example, in a concentration of 2.5 to 25 % by weight.
The incorporation can conveniently be carrried out by the following methods:
- as dry mixture while the additional components or polymer mixtures are being mixed, - by direct addition to the processing apparatus (e.g. extruders, internal mixers, kneaders, three-roll mills, calenders and the like).

CA 02236638 l998-0~-Ol The addition is preferably made direct to the processing apparatus. In this manner it is pos-sible to prepare either masterbatches or the ready polymer compositions.

Polymer compositions according to this invention can be used in different form or can be processed to different products, e.g. foils, fibres, tapes, moulding compositions or profiles.

This invention also relates to the use of a stabiliser mixture B) for thermally stabilising organic polymers, in particular for thermally stabilising food wrappings.

The invention is illustrated by the following Examples.

Examples A: Preparation of the stabiliser mixtures Example A1: Preparation of mixture 101 4 9 of ditrimethylolpropane are added to 59 of a 20 % solution of vitamin E in ethyl acetate.
The resultant suspension is stirred for 2 hours at room temperature. The solvent is then re-moved by evaporation and the solid residue is dried under high vacuum.
5 9 of mixture 101 are obtained in the form of a white (off-white) powder.

Example A2: PreParation of mixture 102 4 g of ditrimethylolpropane and 1 g of vitamin E are melted together in a bulb tube at 150~C
and are rotated for 30 minutes at this temperature.
After cooling to room temperature, the solid residue is ground, giving 5 g of a pale yellow powder.

The mixtures 103-108 are prepared by the process described in Example 1.

Example A3: Preparation of mixture 109 A solution of 1 9 of vitamin E and 39 of ditrimethylolpropane in a mixture consisting of 40 ml of ethyl acetate and 10 ml of methanol is stirred for 2 hours at room temperature. The sol-vents are removed by distillation and the solid residue is dried under high vacuum, giving 4 9 of mixture 109 in the form of a white (off-white) powder.

CA 02236638 1998-0~-01 The mixtures 110 to 114 are obtained as described in Example 3.

Example A4: Preparation of mixture 115 1 g of vitamin E is dissolved in 50 ml of ethyl acetate and then 5 g of calcium stearate are added in one portion. The resultant suspension is stirred for 2 hours at room temperature.
The solvent is removed by distillation and the residue is dried under high vacuum, giving 6 g of mixture 115 in the form of a white powder.

The mixtures 116-126 are obtained by the process described in Example 4.

Example A5: Preparation of mixture 130 A solution of 4 g of ditrimetholpropane in 18 ml of methanol and 5 g of calcium stearate is added to a solution of vitamin E (1 g) in 40 ml of ethyl acetate. The resultant suspension is stirred for 2 hours at room temperature. The solvents are then removed by distillation and the solid residue is dried under high vacuum, giving 10 g of the desired mixture 130 in the form of a white powder.

The mixtures 127-129 and 131-133 are prepared as described in Example 4.

The melting points of the different mixtures are listed in Table 1,2 and 3.

Table 1 Vitamin E / solid polyhydroxy compounds (colour improver) MixtureColour improver Ratio m.p. ~C
colour impr.: vit E
101ditrimethylolpropane 4:1 107 102ditrimethylolpropane 4:1 107 103dipentaerythritol 4:1 221 104dipentaerythritol 3:1 185-218 105tripentaerythritol 4: 1 238 106 mannitol 4: 1 171 107 sorbitol 4:1 97 108ditrimethylolpropane 3:1 107-110 109ditrimethylolpropane 2:1 103 1 10ditrimethylolpropane 1 :1 107-109 111 mannitol 3:1 165-167 11 2 sorbitol 3:1 96 1 13 sorbitol 2:1 92-95 CA 02236638 1998-0~-01 Table 2 vitamin E / acid scavenger mixtures MixtureAcid scavenger Ratio m.p.~C
acid scavenger:
vit E
115calcium stearate 5:1 >280 116calcium stearate 3:1 210 117 zinc stearate 5:1 117 118 zinc stearate 3:1 108 119 DHT 5:1 >280 120 DHT 3: 1 >280 121 ZHT 5:1 >280 122Pationic 12300 3:1 183-194 123Pationic 1240~ 5:1 225 124 Baropol 6180~ 5:1 >280 125 Baropol 6090 5:1 >280 126 Baropol 6190~ 5:1 >280 Table 3 vitamin E / colour improver / acid scavenger ratio: 1 :4:5 MixtureColour improver Acid scavenger m.p.~C
127 triglycerol calcium stearate 110 128dipentaerythritol calcium stearate 290 129tripentaerythritol calcium stearate >280 130ditrimethylolpropanecalcium stearate 115 131ditrimethylolpropanePationic 1230~ 155-206 132 sorbitol Pationic 1230 96-187 133ditrimethylolpropanePationic 1240'D 235 CA 02236638 1998-0~-01 Pationic 1230~, Pationic 1240~, calcium lactate, of PHT Co., Cansas City Baropol MC 6180~, basic magnesium aluminium carbonate, of Barlocher GmbH, Munich.
Baropol MC 6190~, basic calcium aluminium hydroxyborate, of Barlocher GmbH, Munich.
Baropol MC 6090~, basic calcium aluminium hydroxyphosphite, of Barlocher GmbH, Munich.

Eamples B: Working Examples Example B1: HD-Polyethvlene 100 parts by weight of unstabilised HD polyethylene (PE-HD; Eltex A 60-70, of Solvay) are mixed dry for 2 minutes with 0.05 part of calcium stearate and with parts of the stabiliser mix-ture indicated in Table 1. This mixture is then placed in a single-screw extruder (Schwaben-than) having the dimensions D25 mm UD=20 and which is operated at 40 revolutions per minute. The temperature at the feed is 220~C, in zone 2 it is 230~C, in zone 3 it is 240~C and in zone 4 (die) it is also 240~C. Discharge of the extruded material is carried out via a strand die, the strand being cooled in a water bath and then granulated using a strand granulator.
This extrusion is carried out five times under identical conditions, one sample each being taken from the first, third and fifth extrusion to determine the melt flow and yellowness. The yellowness is measured in a spectral photometer suitable for remission measurement using standard illuminant C, UV filter, gloss trap and a detector at 2~ against the primary standard barium sulfate (white,100 % remission) and against the secondary standard, a ceramics plate (84% remission) according to ASTM D1925.
Measurement of the melt flow rate (MFR) is carried out according to ISO 1163. The results are compiled in Table 4.

CA 02236638 l998-0~-Ol Table 4: Results in HD-polyethylene Stab. Mixture Additives % MFR 190~ C/5kg Yellowness Y
No.
1x 3X 5X lx 3X 5X
comparison none 2.0 1.3 1.6 -2.0 -2.5 -2.5 comparison Irganox E 201 0.01 3.5 3.2 3.3 7.9 9.9 10.7 comparison Irganox E 201 0.02 3.5 3.3 3.6 1O.O 12.3 13.8 comparison Irganox E 201 0.05 3.4 3.3 3.6 13.0 17.1 20.0 comparison Irganox E 201 0.02 3.4 3.2 3.4 0.6 1.7 2.2 glycerol (1:1) comparison Irganox E 201 0.04 3.5 3.3 3.5 -0.5 1.4 2.4 glycerol (1:1) 110 Irganox E 201 0.02 3.4 3.2 3.2 0.5 0.9 1.4 DTMP (1:1) 109 Irganox E 201 0.03 3.5 3.4 3.3 0.1 0.5 0.9 DTMP (1 :2) 108 Irganox E 201 0.04 3.5 3.4 3.2 -0.2 0.3 0.7 DTMP (1 :3) 101 Irganox E 201 0.05 3.6 3.5 3.5 -0.6 0.2 0.3 DTMP (1 :4) 111 Irganox E 201 0.04 3.5 3.4 3.4 0.2 0.5 0.9 mannitol (1 :3) 112 Irganox E 201 0.04 3.4 3.3 3.3 0.4 0.7 1.1 sorbitol (1 :3) Example B2: LLDPE-polyethvlene The procedure of Example B1is repeated but replacing HDPE with LLDPE (polyethylene LLD, LL 0209 AP, of BP Chemicals). The results are compiled in Table 5.

CA 02236638 1998-0~-01 Table 5: Results in LLD-polyethylene Stab. mixture Additives % MFR 1 90~ C/5kg Yellowness Y
No.
1 x 3x 5x 1 x 3x 5x comparison none 2.1 1.5 1.2 -1.5 -1.8 -2.1 comparison Irganox E 201 0.01 2.8 2.4 2.2 1.6 2.3 3.0 comparison Irganox E 201 0.02 2.8 2.5 2.3 2.7 4.3 6.5 comparison Irganox E 201 0.05 2.8 2.5 2.3 5.9 10.1 14.5 110 Irganox E 201 0.02 2.8 2.4 2.2 -1.6 -1.4 -1.3 DTMP (1 :1) 109 Irganox E 201 0.03 2.7 2.4 2.3 -1.6 -1.6 -1.4 DTMP (1 :2) 108 Irganox E 201 0.04 2.8 2.5 2.2 -1.8 -1.8 -1.6 DTMP (1 :3) 101 Irganox E 201 0.05 2.8 2.5 2.4 -1.9 -1.8 -1.7 DTMP (1 :4) 111 Irganox E 201 0.04 2.8 2.5 2.3 -1.7 -1.5 -1.3 mannitol (1 :3) 112 Irganox E 201 0.04 2.7 2.5 2.2 -1.6 -1.3 -0.9 sorbitol (1 :3) Irganox E 201 = a-tocopherol (vitamin E), producer: Ciba Spezialitatenchemie.
DTMP = ditrimethylolpropane The numbers of the stabiliser mixtures refer to the mixtures listed in Tables 1-3. Percentages are by weight and are based on the polymer.

Claims (14)

1. A composition, which comprises A) an organic polymeric material and B) a stabiliser mixture consisting b1) of .alpha.-tocopherol, b2) of a solid polyhydroxy compound selected from the group consisting of triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol, or b3) of an acid-binding material or of a mixture consisting of components b2) and b3).
2. A composition according to claim 1, wherein the polymeric organic material A) is polyolefin, polystyrene, PVC, polyamide, polyacrylate or polyester.
3. A composition according to claim 2, wherein the polymeric organic material A) is polyolefin.
4. A composition according to claim 1, wherein the solid polyhydroxy compound is ditrimethylolpropane, dipentaerythritol, tripentaerythritol.
5. A composition according to claim 1, wherein the acid-binding material is an alkaline earth salt or zinc salt of a C3-C18carboxylic acid, alkaline earth/aluminium carbonate, alkaline earth/aluminium hydroxyborate, alkaline earth/aluminium hydroxyphosphite or zeolite.
6. A composition according to claim 1, which comprises A) an organic polymeric material and B) a stabiliser mixture consisting b1) of .alpha.-tocopherol and b2) of a solid polyhydroxy compound selected from the group consisting of triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol.
7. A composition according to claim 1, which additionally comprises a UV absorber or a sterically hindered amine, or both.
8. A composition according to claim 1, wherein component b1) is present in an amount of 0.005 to 2 % by weight, based on the polymer A).
9. A composition according to claim 1, wherein component b2) is present in an amount of 0.005 to 5 % by weight, based on the polymer A).
10. A composition according to claim 1, wherein the ratio of b1) to b2) is from 10:1 to 1:10.
11. A composition according to claim 1, wherein component b3) is present in an amount of 0.005 to 5 % by weight, based on the polymer A).
12. A stabiliser mixture, which consists b1) of .alpha.-tocopherol, b2) of a solid polyhydroxy compound selected from the group consisting of triglycerol, ditrimethylolpropane, dipentaerythritol, tripentaerythritol, D-mannitol, D-sorbitol and xylitol, or b3) of an acid-binding material or of a mixture consisting of components b2) and b3).
13. Use of a stabiliser mixture according to claim 12 for thermally stabilising organic polymers.
14. Use of a stabiliser mixture according to claim 12 for thermally stabilising food wrappings.
CA002236638A 1997-05-05 1998-05-01 Vitamin e formulations for stabilising polymeric organic materials Abandoned CA2236638A1 (en)

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