WO2010069854A2 - Modified polyolefin waxes - Google Patents

Abstract

Described is a method for modifying the thermal softening behaviour of a polyolefin wax, which comprises the incorporation into the wax of at least one compound of the formula (I) wherein Q is a C₃-C₁₂alkyltriyl, a tris(C₁-C₈alkylene)amine, a C₃-C₁₂cycloalkyltriyl or is of the formula (II), (III) or (IV); X₁, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO-O-, -O-CO-NH-, - NH-CO-, -CO-NH, -COO- or -0-; R₁, R₂ and R₃ are various unsubstituted or substituted aliphatic or aromatic radicals.

Description

Modified Polyolefin Waxes

The present invention relates to a method for the modification of the thermal softening behaviour of a polyolefin wax.

Most reported modifications of polyolefin waxes involve chemical reactions. These chemical modifications - like saponification, oxidation, esterification or grafting - are well-known processes and refer mainly to polar polyolefin waxes.

These polar polyolefin waxes are used for instance in emulsion systems like fruit-coating emulsions, dry-bright emulsions or pour point depressants of fuel and crude oils. Non-polar polyolefin waxes are hardly useable for these applications.

Polar polyolefin waxes can also be based on copolymers of non-polar olefins, e.g. ethylene or propylene, with polar monomers, e.g. acrylic acid, acrylic acid derivatives or vinyl acetate.

Physical modification of polyolefin waxes can be performed either by blending of two or more waxes (whereas said blends are known then as wax preparations) or by the incorporation of additives.

The blending of waxes is generally recommended and predictable, when the waxes are compatible with each other, which limits the scope of possibilities. The result will usually be a product with properties lying between those of the waxes used for the blending. A practical example is the blending of polyethylene waxes with paraffin waxes, which increase - in regard to the pure paraffin wax - the thermal resistance and other temperature-related properties. These (blended) wax preparations are used for instance to increase the temperature resistance of care product pastes or to increase the melting point of hydrocarbon based coatings for packaging materials.

The physical modification of polyolefin waxes by incorporation of additives is seldom reported. Incorporation of suitable additives avoids the compatibility issue in the case of blending and the likelihood is higher to achieve properties or combinations of properties beyond the limits of the mere blending of two given polyolefin wax grades. The incorporation of additives into the polyolefin wax has got the advantage that it avoids the need to produce the new polyolefin wax grade by chemical modification or to match the requested specific technical feature by blending of different polyolefin wax grades.

The modification of the thermal softening behaviour of a polyolefin wax is of relevance in industrial applications, for example for obtaining hotmelt adhesive systems with higher thermal resistance and with less or no dripping. Another example are candles with adjusted dripping behavior. In surface protection applications like for example floor polishes, car bodies and fabrics, higher working temperatures without softening or dirt adhesion can be achieved by using polyolefin waxes with higher drop points or softening points respectively. Furthermore, polyolefin waxes with higher drop points or softening points respectively contribute to higher attrition or abrasion temperatures of printing inks with clear advantages for the use or storage of such inks.

The modification of the particle size, typically through a micronization process, results in micronized polyolefin waxes or nanoparticle polyolefin waxes. Such polyolefin waxes are used for example as carriers and encapsulation systems in the cosmetic and pharmaceutical areas. However, they can not be considered as modified waxes as such due to the fact that their intrinsic structure is not changed by the micronization process - apart from the possible slight degradation that may occur during the micronization process due to mechanical strain.

Although existing polyolefin wax grades cover many needs and have got a wide range of technical features, certain combinations of properties remain difficult to obtain. For instance, a drop point of 170 ⁰C for a polyethylene wax is very difficult to achieve so far without chemical modification of said polyethylene wax. Polyethylene waxes are above their melting point low viscous, fast flowing liquids.

Now, it has been found that incorporation of certain additives modifies beneficially the thermal softening behaviour of polyolefin waxes.

The present invention relates in particular to a method for modifying the thermal softening behaviour of a polyolefin wax, which comprises the incorporation into the wax of at least one compound of the formula (I) R₁ X₁

_X/^Q-_X (i)

R K₃^ R K₂ wherein

Q is a C₃-Ci₂alkyltriyl, a C₃-Ci₂alkenyltriyl, a tris(Ci-C₈alkylene)amine, a C₃-Ci₂cycloalkyltriyl or is

o

;

Xi, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO-O-, -O-CO-NH-, -

NH-CO-, -CO-NH, -COO- or -0-;

Ri, R₂ and R₃ are independently from each other

Ci-C₂oalkyl unsubstituted or substituted by one or more hydroxyl or halogen, C₂-C₂₀alkenyl unsubstituted or substituted by one or more hydroxyl or halogen,

C₃-C₂₀alkinyl,

C₂-C₂₀alkyl interrupted by oxygen or sulfur,

C₃-Ci₂cycloalkyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, (C₃-Ci₂cycloalkyl)-Ci-Ci₀alkyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, bis[C₃-Ci₂cycloalkyl]-Ci-Ci₀alkyl unsubstituted or substituted by one or more d-

C₂₀alkyl, a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C₂₀alkyl, phenyl unsubstituted or substituted by one or more radicals selected from CrC₂₀alkyl, Ci-C₂₀alkoxy, Ci-C₂₀alkylamino, di(Ci-C₂₀alkyl)amino, hydroxy, nitro, halogen or d-

Cβhaloalkyl, phenyl-Ci-C₂oalkyl unsubstituted or substituted by one or more radicals selected from Ci-C₂₀alkyl, C₃-Ci₂cycloalkyl, phenyl, CrC₂₀alkoxy, hydroxy, halogen or CrC₈haloalkyl, phenylethenyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, phenyloxymethyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, biphenyl-(Ci-Ci_Oalkyl) substituted by one or more Ci-C₂₀alkyl, naphthyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, naphthyl-Ci-C₂₀alkyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, naphthyloxymethyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, biphenylenyl, fluorenyl, anthryl, 5- to 6-membered heterocyclic radical unsubstituted or substituted by one or more Cr C₂₀alkyl, or tri-(Ci-Cioalkyl)-silyl-(Ci-Ci_Oalkyl).

An example of C₃-C₁₂alkyltriyl (preferably C₃-C₆alkyltriyl) is propane-1 ,2,3-triyl.

An example of C₃-Ci₂alkenyltriyl (preferably C₃-C₆alkenyltriyl) is propene-1 ,2,3-triyl.

Examples of tris-(Ci-C8alkylene)amine are tris(methylene)amine, tris-(1 ,2-ethylene)amine, and tris-[1 ,2-(2-methyl)ethylene]amine.

Examples of C₃-Ci₂cycloalkyltriyl (preferably C₃-C₆cycloalkyltriyl, particularly C₅- Cβcylcoalkyltriyl) are cyclohexane-1 ,3,5-triyl and cyclohexane-1 ,2,4-triyl.

Preferred Ci-C₂oalkyl, e.g. branched C₃-C₂₀alkyl, are for example Ci-Ci_Oalkyl, CrC₆alkyl, d- C₄alkyl and C₃-C₆alkyl, which are unsubstituted or substituted by one or more hydroxy or halogen, for example 1 to 3. Examples are ethyl, n-propyl, 1-methylethyl, n-butyl, 2- methylpropyl, 1-methylpropyl, tert-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1-dimethylpropyl, 1-ethylpropyl, tert-butylmethyl, hexyl, 1-methylpentyl, heptyl, isoheptyl, 1- ethylhexyl, 2-ethylpentyl, 1-propylbutyl, octyl, 1 ,1 ,3,3-tetramethylbutyl, nonyl, isononyl, neononyl, 2,4,4-trimethylpentyl, undecyl, tridecyl, pentadecyl, heptadecyl, hydroxymethyl, 1- hydroxyethyl, dichloromethyl, 1-bromo-2-methylpropyl and pentafluoroethyl.

Preferred C₂-C₂oalkenyl are C₂-C₆alkenyl and C₂-C₄alkenyl, which are unsubstituted or substituted by one or more hydroxy or halogen, for example 1 to 3. Examples are 9-decenyl, 8-heptadecenyl and H-hydroxy-8-heptadecenyl.

Preferred C₃-C₂₀alkinyl are C₃-Ci₈alkinyl and C₃-Ci₂alkinyl. Examples are propargyl, but-3- inyl, hex-5-inyl, oct-7-inyl, dec-9-inyl, dodec-1 1-inyl, tetradec-13-inyl, hexadec-15-inyl, octadec-17-inyl and eicos-19-inyl.

Preferred C₂-C₂₀alkyl interrupted by oxygen are C₂-C₂₀alkyl interrupted by 1 to 10, particularly 1 to 5, for example 1 oxygen atom. The number of carbon atoms is for example 2 to 10, preferably 2 to 6, for example 2 to 4. Examples are t-butoxymethyl, t-butoxyethyl, t-butoxypropyl and t-butoxybutyl.

Preferred for C₂-C₂oalkyl interrupted by sulfur are numbers for sulfur and carbon atoms in analogy to the alkyl groups interrupted by oxygen atoms. Examples are (H₃C)₃C-S-CH₂-, (H₃C)₃C-S-C₂H₄-, (H₃C)₃C-S-C₃H₆- and (H₃C)₃C-S-C₄H₈-.

Preferred C₃-Ci₂cycloalkyl are C₃-C₆cycloalkyl, particularly C₅-C₆cycloalkyl, which are unsubstituted or substituted by one or more, e.g. 1 , 2, 3 or 4, CrC₂₀alkyl, preferably d- C₄alkyl. Examples are cyclopropyl, 3-methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3- methylcyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl and cycloheptyl.

Preferred (C₃-Ci₂cycloalkyl)-CrCi₀alkyl are (C₃-C₆cycloalkyl, particularly C₅-C₆cycloalkyl)-Ci- Cio-(preferably Ci-C₄)alkyl, which are unsubstituted or substituted by one or more, e.g. 1 , 2 or 3, Ci-C₂₀alkyl, preferably Ci-C₄alkyl. Examples are cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl, 2-cycohexylethyl, 3-cyclohexylpropyl, 4-cyclohexylbutyl and (4- methylcyclohexyl)methyl.

Preferred bis[C₃-Ci₂cycloalkyl]-CrCi₀alkyl are bis(C₃-C₆cycloalkyl, particularly C₅- C₆cycloalkyl)-CrCio-(preferably Ci-C₄)alkyl, which are unsubstituted or substituted by one or more, e.g. 1 , 2 or 3, Ci-C₂₀alkyl, preferably Ci-C₄alkyl. An example is dicyclohexylmethyl.

Examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C₂₀alkyl, e.g. 1 , 2 or 3 Ci-C₄alkyl, are

and

Examples of phenyl unsubstituted or substituted by one or more radicals, e.g. 1 , 2 or 3 radicals, selected from d-C₂oalkyl (preferably CrC₉alkyl, particularly d-C₄alkyl), Ci-C₂oalkoxy (preferably Ci-C₄alkoxy), Ci-C₂oalkylamino (preferably Ci-C₆alkylamino, particularly Ci-C₄alkylamino), di(Ci-C₂oalkyl)amino (preferably di(Ci-C₈alkyl)amino, particularly di(Ci-C₄alkyl)amino), hydroxy (preferably 1 to 2, particularly 1 ), nitro, halogen (preferably 1 to 2, particularly 1 ) or d-C₈haloalkyl (preferably Ci-C₄haloalkyl, particularly halomethyl) are phenyl, 3-methylphenyl, 3-methoxyphenyl, 4-methylphenyl, 4-ethylphenyl, 4-propylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 4-isopropoxyphenyl, 2,3-dimethoxyphenyl, 2-nitrophenyl, 3-methyl-6-nitrophenyl, 4-dimethylaminophenyl, 2,3- dimethylphenyl, 2,6-dimethylphenyl, 2,4-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 3 ,5-d i-tert-butyl-4- hydroxyphenyl, 2,3-dichlorophenyl, 3,4-dichlorophenyl, 2,3,5,6-tetrafluoro-p-tolyl, 2,4-bis- [trifluoromethly]phenyl and 3,5-bis[trifluoromethyl]phenyl.

Examples of phenyl-Ci-C₂₀alkyl (preferably phenyl-Ci-C₄alkyl) unsubstituted or substituted by one or more radicals, e.g. 1 , 2 or 3 radicals, selected from CrC₂₀alkyl (preferably CrC₉alkyl, particularly Ci-C₄alkyl), C₃-Ci₂cycloalkyl (preferably C₃-C₆cycloalkyl, particularly C₅- C₆cycloalkyl), phenyl, d-C₂₀alkoxy (preferably Ci-C₄alkoxy), hydroxy, halogen or d- Cβhaloalkyl (preferably Ci-C₄haloalkyl, particularly halomethyl) are benzyl, α- cyclohexylbenzyl, diphenylmethyl, 1-phenylethyl, α-hydroxybenzyl, 2-phenylethyl, 2- phenylpropyl, 3-phenylpropyl, 3-methylbenzyl, 3,4-dimethoxybenzyl, 2-(3,4- dimethoxyphenyl)ethyl and 3,5-bis[trifluoromethyl]benzyl.

An example of phenylethenyl unsubstituted or substituted by one or more CrC₂oalkyl, e.g. 1 , 2 or 3 Ci-C₄alkyl, is 2-(4-methylphenyl)ethenyl.

Examples of phenyloxymethyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, e.g. 1 , 2 or 3 CrC₄alkyl, are phenoxymethyl and (4-methylphenoxy)methyl. An example of biphenyl-(Ci-Ci_Oalkyl) unsubstituted or substituted by one or more Ci-C₂oalkyl, e.g. 1 , 2 or 3 CrC₄alkyl, is 4-biphenylmethyl.

Examples of naphthyl unsubstituted or substituted by one or more Ci-C₂oalkyl, e.g. 1 , 2 or 3 CrC₄alkyl, are 1 -naphthyl and 2-naphthyl.

Examples of naphthyl-CrC₂oalkyl (preferably naphthyl-Ci-C₉alkyl, particularly naphthyl-d- C₄alkyl) unsubstituted or substituted by one or more Ci-C₂oalkyl, e.g. 1 , 2 or 3 Ci-C₄alkyl, are 1-naphthylmethyl and 2-naphthylmethyl.

An example of naphthoxymethyl unsubstituted or substituted by one or more CrC₂₀alkyl, e.g. 1 , 2 or 3 CrC₄alkyl, is 1 -naphthoxymethyl.

Examples of biphenylenyl, fluorenyl or anthryl are 2-biphenylenyl, 9-fluorenyl, 1-fluorenyl or 9-anthryl, respectively.

Examples of a 5- to 6-membered heterocyclic radical, which preferably contains 1 to 3, for example 1 to 2, especially 1 nitrogen atom, sulfur atom or / and oxygen atom, unsubstituted or substituted by one or more Ci-C₂₀alkyl, e.g. 1 , 2 or 3 Ci-C₄alkyl, are 3-pyridinyl, 4- pyridinyl, 2-hydroxypyridin-3-yl, 2-furyl, 3-furyl and 1-methyl-2-pyrrolyl.

Examples of halogen are fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, preferably chlorine and fluorine atoms.

Examples of a Ci-C₈haloalkyl (preferably Ci-C₄haloalkyl, particularly halomethyl) are dichloromethyl, difluoromethyl and trifluoromethyl.

Prefered is furthermore a method according to this invention wherein

Q is of the formula or

Xi, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO-O, -O-CO-N-, NH-

CO- or -CO-NH-;

R-i, R₂ and R₃ are independently from each other CrCi₂alkyl unsubstituted or substituted by 1 , 2 or 3 hydroxy or halogen,

C₂-C₂oalkenyl unsubstituted or substituted by 1 , 2 or 3 hydroxy or halogen, C₂-Ci₀alkyl interrupted by oxygen,

C₃-C₆cycloalkyl unsubstituted or substituted by 1 , 2, 3 or 4 d-C₄alkyl, (C₃-C₆cycloalkyl)-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl, bis-[C₃-C₆cycloalkyl]-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl,

phenyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from Ci-C₄alkyl, d-

C₄alkoxy, Ci-C₄alkylamino, di-(CrC₄alkyl)-amino, hydroxyl, nitro, halogen and d-

C₄haloalkyl, phenyl-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from d-

C₄alkyl, C₃-C₆cycloalkyl, phenyl, Ci-C₄alkoxy, hydroxy, halogen and Ci-C₄haloalkyl, phenylethenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl, phenyloxymethyl unsubstituted or substituted by 1 ,2 or 3 Ci-C₄alkyl, biphenyl-(Ci-Cioalkyl) substituted by 1 , 2 or 3 d-C₄alkyl, naphthyl unsubstituted or substituted by 1 , 2 or 3 d-dalkyl, naphthyl-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 d-dalkyl, naphthyloxymethyl unsubstituted or substituted by 1 , 2 or 3 d-dalkyl, biphenylenyl, fluorenyl, anthryl,

3-pyridinyl, 4-pyridinyl, 2-hydroxypyridin-3-yl, 2-furyl, 3-furyl, 1-methyl-2-pyrrolyl, or tri-(d-do)alkyl-silyl-(d-d_oalkyl).

More preferred is a method according to this invention wherein

Q is of the formula or

Xi, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO- or -CO-NH-; Ri, R₂ and R₃ are independently from each other C₃-Ci₂alkyl,

C₃-Ci₀alkyl interrupted by oxygen,

C₃-C₆cycloalkyl unsubstituted or substituted by 1 , 2, 3 or 4 d-C₄alkyl, (C₃-C₆cycloalkyl)-Ci-Ci₀alkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl, phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl, phenyl-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from d-

C₄alkyl and Ci-C₄alkoxy, biphenyl-(Ci-Ci_Oalkyl), naphthyl-Ci-Cioalkyl, or tri-(Ci-Ci₀alkyl)-silyl-(Ci-C₅)alkyl.

Even more preferred is a method according to this invention wherein

Q is of the formula or

Xi, X₂ and X₃ are independently from each other -NH-CO- or -CO-NH-; Ri, R₂ and R₃ are independently from each other C₃-Ci₂alkyl.

Especially preferred is a method according to this invention wherein

Q is of the formula or

Xi, X₂ and X₃ are -NH-CO-; Ri, R₂ and R₃ are the same C₃-Ci₂alkyl.

Especially further preferred is a method according to this invention wherein

Q is of the formula

Xi, X₂ and X₃ are -NH-CO-;

Ri, R₂ and R₃ are the same and selected from 2-methylpropyl, 1-methylpropyl, 1-methylbutyl and 1 ,1-dimethylethyl.

Especially preferred is a method according to this invention wherein

Q is of the formula or

Xi, X₂ and X₃ are -CO-NH-; Ri, R₂ and R₃ are the same C₃-Ci₂alkyl.

Especially further preferred is a method according to this invention wherein

Q is of formula Xi, X₂ and X₃ are -CO-NH-;

Ri, R₂ and R₃ are the same and selected from n-butyl, 3-methylbutyl, 2-methylbutyl, 1- propylbutyl and 1 ,1 ,3,3-tetramethylbutyl.

Furthermore preferred is a method according to this invention wherein

Q is of the formula Xi, X₂ and X₃ are -CO-NH-; Ri, R₂ and R₃ are the same C₃-Ci₂alkyl.

Especially preferred is a method according to this invention wherein

Q is of formula

Xi, X₂ and X₃ are -CO-NH-; R-i, R₂ and R₃ are the same and selected from n-butyl, 3-methylbutyl, 2-methylbutyl, 1- propylbutyl and 1 ,1 ,3,3-tetramethylbutyl.

The compounds of formula I are incorporated into the polyolefin wax in an overall concentration in the polyolefin wax of 0.005% to 3%, preferably 0.015% to 0.3% by weight.

The polyolefin wax, which is modified in its thermal softening behaviour, might contain further additives out of the groups listed below in a concentration range, which does not adversely effect the invention.

- antioxidants

- UV absorbers and light stabilisers

- metal deactivators

- phosphites and phosponites - hydroxylamines

- nitrones

- thiosynergists

- peroxide scavengers

- benzofuranones and indolinones - polyamide stabilisers

- basic co-stabilisers

- nucleating agents

- other additives

More detailed examples of these further additives are listed below.

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, 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-dimethyl-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 hydroquinones, 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-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-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-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methy- lenebis(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-methylphenyl)-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-hydroxy-2-methylphenyl)pentane.

1.7. Q-, 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-S^-di-tert-butyM-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)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-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl 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.

1.10. 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-tri- azine, 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-hydroxyben- zyl)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-hydroxy- phenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate.

1.1 1. Benzylphosphonat.es, 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-hy- droxybenzylphosphonate, dioctadecyl-S-tert-butyl^-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. 1.13. Esters of β-(3,5-di-tert-butyl-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.

1.14. Esters of β-(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric 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, 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; 3,9-bis[2-{3-(3-tert- butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1 ,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]- undecane.

1.15. Esters of β-(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with 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, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with 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, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau- gard^®XL-1 , supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-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'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-N'-phe- nyl-p-phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di- sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl- amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph- thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl- aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino- methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra- methyl-4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methylphenyl)amino]ethane, 1 ,2-bis(phenyl- amino)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-octyldiphenyl- amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl- diphenylamines, 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-octylphenothiazines, a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetra- methylpiperid-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 light 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-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(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-ethylhexyl- oxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1 ,1 ,3,3- tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu- tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol

300; [R-CH₂CH₂-COO-CH₂CH₂-^- , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri-

azol-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]ben- zotriazole.

2.2. 2-Hvdroxybenzophenones, 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.

2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 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 α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycin- namate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline. 2.5. Nickel compounds, for example nickel complexes of 2,2'-thiobis[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-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6. Sterically 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-piperi- dyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)- 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-di- chloro-1 ,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetra- methyl-4-piperidyl)-1 ,2,3,4-butanetetracarboxylate, 1 ,1'-(1 ,2-ethanediyl)-bis(3,3,5,5-tetrame- thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl- piperidine, 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 -octyl- oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succi- nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene- diamine 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 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-tetrame- thyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 -(2,2,6, 6-tetramethyl-4-piperidyl)pyr- rolidine-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 condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6- dichloro-1 ,3,5-triazine, a condensate of 1 ,2-bis(3-aminopropylamino)ethane and 2,4,6-tri- chloro-1 ,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1 ,6-hexanediamine and 2,4, 6-trichloro-1 ,3,5-triazine as well as N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1 , 2,2,6,6- pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9, θ-tetramethyl^-cycloundecyl-i-oxa- 3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1 ,1-bis(1 ,2,2,6, 6-pentamethyl-4- piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetrame- thyl-4-piperidyl)hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1 ,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4- piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1 ,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 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, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1 ,3,5-triazines, 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-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-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-dimethyl- phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hy- droxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hy- droxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1 ,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine.

3. Metal deactivators, 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, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)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-tris(tert-butylphenyl)pentaerythritol diphosphite, tristea- ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6- isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1 ,3,2-dioxaphosphocin, bis(2,4-di-tert- butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1 ,3,2-dioxaphosphocin, 2,2',2"-nitrilo- [triethyltris(3,3',5,5'-tetra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te- tra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)- 1 ,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos^®168, Ciba-Geigy), tris(nonylphenyl) phosphite,

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-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.

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

8. Peroxide scavengers, for example esters of β-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(β- dodecylmercapto)propionate.

9. Benzofuranones and indolinones, for example those disclosed 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-431661 1 ;

DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 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-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7- di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzo- furan-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphe- nyl)-5,7-di-tert-butylbenzofuran-2-one.

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

1 1. 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 zinc pyrocatecholate. 12. Nucleating agents

12.1 inorganic substances, for example talcum, metal oxides like titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals.

12.2 mono- or polycarboxylic acids and the salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, sodium benzoate, di-sodium salt of cis-endo-bicyclo(2.2.1 )heptane 2,3-dicarboxylic acid (= Chemical Abstracts Registry No. 351870-33-2), commercially available as Hyperform HPN-68 (RTM), salts of rosin, or abietic acid, for example commercially available as Pinecrystal KM-1300 (RTM) or Pinecrystal KM-1600 (RTM), respectively.

12.3 polymeric compounds, for example ionic copolymers (ionomers), polyvinylcyclohexane, poly-(1 ,2-ethylene-1 ,3-cyclopentylene).

12.4 aromatic sorbitol acetals, for example

• 1 ,3:2,4-bis(benzylidene)sorbitol, commercially available as lrgaclear D (RTM), Millad 3905 (RTM) and Gel All D (RTM). • 1 ,3:2,4-bis-(4-methylbenzylidene)sorbitol, commercially available as lrgaclear DM (RTM), Millad 3940 (Milliken, RTM), NC-6 (Mitsui, RTM) and Gel All MD (New Japan Chemical, RTM).

• 1 ,3:2,4-bis-(3,4-dimethylbenzylidene)sorbitol, commercially available as Millad 3988 (RTM) • 1 ,3:2,4-bis-(4-ethylbenzylidene)sorbitol, commercially available as NC-4 (Mitsui, RTM)

• 1 ,3:2,4-bis-(4-chlorobenzylidene)sorbitol

12.5 Nucleating agents based upon salts of phosphoric acid, for example

• 2,2'-Methylen-bis-(4,6-di-tert-butylphenyl)phosphate, commercially available as Adeka Stab NA1 1 (RTM) containing sodium ions, Adeka Stab NA21 (RTM) containing aluminium hydroxide ions, Adeka Stab Na71 containing lithium ions.

12.6 Nucleating agents based upon carboxy aluminum-hydroxide, for example aluminum hydroxy-bis-[4-tert-butylbenzoate], commercially available as Sandostab 4030 (RTM). 12.7 Other nucleating agents, for example Zinc (II) monoglycerolate commercially available as lrgastab Na 287 (Ciba, RTM), as Prifer 3881 (RTM) and as Prifer 3888 (RTM).

Especially preferred are 1 ,3:2,4-bis-(3,4-dimethylbenzylidene)sorbitol

1 ,3:2,4-bis-(4-methylbenzylidene)sorbitol

and 1 ,3:2,4-di(benzylidene)sorbitol

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

The weight ratio of the above described further additives to the overall amount of the components according to formula I is preferably 1 :100 to 100:1 , for example 1 :90 to 90:1 , 1 :80 to 80:1 , 1 :70 to 70:1 , 1 :60 to 60:1 , 1 :50 to 50:1 , 1 :40 to 40:1 , 1 :30 to 30:1 , 1 :20 to 20:1 , 1 :10 to 10:1 , 1 :5 to 5:1 , 1 :4 to 4:1 , 1 :3 to 3:1 , 1 :2 to 2:1 or 1 :1.

A comprehensive definition and review on waxes is given, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A-28, VCH Verlagsgesellschaft mbH, D-69451 Weinheim, 1996 (in particular, see pages 104 ff. therein), which is incorporated herewith by reference.

The waxes of the present invention are non-polar or polar polyolefin waxes.

Polyolefin waxes are industrially produced by the following main processes: The thermomechanical degradation process is based on the reduction of molecular weight of polyolefin polymers (e.g. LDPE, HDPE, i-PP) in the extruder at around 400⁰C under nitrogen atmosphere.

The direct polymerization of the monomers, like for example ethylene or propylene, is employed at high scale and can be realized in two ways:

(a) A high pressure process, whereby the olefin - e.g. ethylene - undergoes radical polymerization in an autoclave or a tubular reactor. Organic peroxide or oxygen is used as initiator. Targeted average molecular weight, molecular weight distribution and level of branching are obtained by proper setting of pressure (150-320 MPa), temperature (200- 300⁰C) and hydrogen amount as molecular weight regulator.

(b) A low pressure process, whereby in solution metallo-organic catalysts are employed. The use of Ziegler-Natta or metallocene catalysts provides the possibility to polymerize ethylene and propylene by coordination polymerization. The control of the properties of the waxes produced with this process is achieved by suitable temperature, through the selection of the catalyst and the hydrogen amount. Since metallocene catalysts possess only one active position for polymerization reaction (single-site), polyolefin waxes can be obtained with sharper property profiles than it is possible with conventional Ziegler-Natta catalysts.

Appropriate methods for preparing homo- and copolymeric olefin waxes are described by way of example in Ullmann's Encyclopedia of Industrial Chemistry, 5^th Ed., Vol. A 28, Weinheim 1996 in chapter 6.1.1 / 6.1.2 (high-pressure polymerization), chapter 6.1.3 (Ziegler-Natta polymerization, polymerization using metallocene catalysts) and chapter 6.1.4 (thermal processes for reducing molecular weight), pp.146-154 or in the electronic version of Ullmann's Encyclopedia of Industrial Chemistry, 6^th Edition, Electronic Release; Wiley-VCH: Weinheim, 2002.

Suitable polyolefin waxes of this invention include degradation waxes, prepared by thermal degradation of ethylene or 1 -olefin homopolymers and copolymers, polyethylene or polypropylene for example. Further suitable waxes are obtained by polymerization in a free-radical process or using Ziegler-Natta or metallocene catalysts. Examples are homopolymers of ethylene or of higher 1 -olefins or their copolymers with one another. The employed 1 -olefins are linear or branched olefins having 3-18 C atoms, preferably 3-6 C atoms. The 1 -olefins may also have aromatic substitution conjugated with the olefinic double bond. Examples of 1 -olefins are propene, 1-butene, 1-hexene, 1-octene, 1-octadecene or styrene. It is also possible for these 1 -olefins to contain polar functions such as ester groups or acid groups, for example vinyl acetate, acrylic acid, methyl acrylate or ethyl acrylate.

Also suitable are polar polyolefin waxes prepared by chemical modification of aforementioned polyolefin waxes. The chemical modification is accomplished by processes, which are known in principle. For example, oxidation with oxygen-containing gases like air and / or by grafting with α,β-unsatu rated acids or their derivatives. These are for example acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, fumaric acid, maleic anhydride, dimethyl maleate or diethyl maleate. Further feasible grafting agents are substituted and / or unsubstituted styrenes and / or vinylsilanes. Suitable polar polyolefin waxes are also accessible by oxidative degradation of non-waxlike polymers of relatively high molecular mass, such as preferably polyethylene, polypropylene or copolymers thereof.

The polar polyolefin waxes are preferably polyethylene, polypropylene or copolymers of ethylene or propylene, which have been converted into the polar polyolefin waxes by oxidation or by grafting with monomers containing vinyl groups. These monomers containing vinyl groups are preferably acrylic acid derivatives, methacrylic acid derivatives, maleic acid derivatives, fumaric acid derivatives, styrene and / or silicon- containing olefins.

The preferred polyolefin waxes in this invention are non-polar.

The nonpolar polyolefin waxes are preferably homopolymers and copolymers of ethylene, propylene and / or other olefins.

The nonpolar polyolefin waxes are preferably homopolymers and copolymers of ethylene or propylene with C₃-C₂O-I -olefins. The nonpolar polyolefin waxes in this invention are preferably either polyethylene-based, i.e. a weight majority is made up of polyethylene, or polypropylene-based, i.e. a weight majority in the wax is made up of polypropylene.

The nonpolar polyolefin waxes are preferably homopolymers or copolymers of ethylene or propylene.

The modification of the thermal softening behaviour of polyolefin waxes is also of special importance in the case of low melting metallocene polyethylene or metallocene polypropylene waxes. Such types of polyolefin waxes possess a relatively sharp melting point within a narrow temperature range. These metallocene polyethylene or metallocence polypropylene waxes turn from a solid into a fast flowing liquid, which is to a certain extent an untypical behaviour for a wax. The incorporation of at least one compound of formula I allows the extension of the application area of such a wax without the need of employing chemical modifications - like for example the change of the average molecular weight. This means that the melting point can be exceeded up to the drop point or softening point respectively without entering the quickly flowing state. Hence, the drop point or softening point respectively can be settled by a physical modification by incorporation of an additive without the need to resort to chemical modification of the polyolefin wax grade itself.

The nonpolar polyolefin waxes are preferably homopolymers and copolymers of ethylene or propylene or copolymers of ethylene and propylene which are prepared by the Ziegler-Natta process or the metallocene process.

The average molecular weight (Mw) of the polyolefin waxes of this invention ranges from 400 to 20000 g/mol with number average molecular weight (Mn) 500 to 5000 g/mol, preferably from 1500 to 8000 g/mol with number-average molecular weight from 2000 to 4000 g/mol.

The various types of polyolefin waxes can be classified according to their physical and mechanical properties, among others their melting point, drop point or softening point respectively, melt viscosity, crystallinity, density and hardness. These macroscopic properties depend hereby on average molecular weight, molecular weight distribution (polydispersity), chain branching, tacticity in case of polypropylene and monomer ordering in case of copolymers. These properties can be controlled during the production process. By way of example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A 28, Weinheim 1996, Chapter 6.1.5, p. 155 gives appropriate cases. The drop point of a wax is the temperature, at which upon slow heating the first drop of a wax, which is placed in a nipple with a calibrated hole (diameter 2.8 mm), drips through the hole. Only waxes with low melt viscosity (i.e. with viscosity up to approx. 2000 mPa.s at a temperature approx. 10⁰C above the drop point) and with clear dripping can be measured by this method.

For waxes that have higher melt viscosity and therefore can not form droplets, which can drip through the nipple hole, the appropriate method is the softening point measurement. The softening point is defined as the temperature at which the melt, passing through a hole of 6.35 mm diameter, is 20 mm long.

The drop point and softening point are empiric methods without clear physical background. They depend on the heating rate, the preparation of the probe and on the geometry of the crucible.

The measurement is described in standards ASTM D3954-94 (2004) [standard test method for dropping point of waxes] or ASTM D3104-99 (1995) [standard test method for softening point of pitches - Mettler softening point method] respectively. The methods provide reproducible results.

The drop points or softening points respectively of polyolefin waxes are typically between 80⁰C and 170⁰C, according to the respective wax grade. There are many parameters influencing the values, especially the average molecular weight, the molecular weight distribution (polydispersity), the polymer recipe, the chain branching and the tacticity in case of polypropylene.

Both 'drop point' and 'dropping point' expressions are used and found in the literature. The locution of 'drop point' is used in this document.

It is preferable that the drop point or the softening point respectively of the polyolefin waxes ranges from 75°C to 215°C.

The melt viscosity - measured 10⁰C above the drop point or the softening point respectively - of the polyolefin waxes ranges usually from 20 to 70000 mPa.s The acid numbers of the polyolefin waxes ranges from 0 to 120 mg KOH/g, whereupon the acid numbers are determined according to DIN EN ISO 21 14.

The polyolefin waxes can be used in the form of pellets, flakes, fine grains, powder or micronizate.

The additive compounds according to formula I of this invention can be used in every physical form, preferably as powder.

The preferred method to modify the thermal softening behaviour of polyolefin waxes by incorporation of at least one compound of formula I is confirmed by an enhancement of the drop point for polyethylene or polyethylene-based waxes or by an enhancement of the softening point for polypropylene or polypropylene-based waxes respectively.

Preferably, the method of this invention results is an enhancement of the drop point or the softening point respectively, which is more than 5°C but less than 90⁰C, particularly more than 10⁰C but less than 80°C, for example more than 20⁰C but less than 80°C, compared to the value for the same polyolefin wax without incorporation of a compound of formula I.

Compounds of formula I can be added into the liquid wax, more specifically into the molten wax, and for instance dispersed with a high speed mixer or any system liable to ensure homogenous mixing of the additive phase in the wax. The mixing temperature should be higher than the drop point or the softening point respectively of the pure polyolefin wax, for instance 20°C higher. The duration of the mixing phase should last long enough to obtain homogenous distribution, but short enough to avoid degradation due to thermal and / or mechanical strain. After mixing, the polyolefin wax with incorporated additive is cooled down.

Preferred is a method according to this invention wherein at least one compound of formula I is homogenously incorporated into the polyolefin wax which is in the liquid state.

More preferred is a method according to this invention wherein at least one compound of formula I is homogenously incorporated into the polyolefin wax which is in the liquid state at a temperature superior to the drop point or softening point respectively of the polyolefin wax. Preferably, homogenous incorporation is effected by high shear mixing at a temperature superior to the drop point or to the softening point respectively of the polyolefin wax. Polyolefin waxes are used in a wide range of applications. In most cases, their performance lie on functionalities such as matting, hydrophobing, dispersion, release, viscosity control, lubrication, protection, smoothing, binding, plasticizing, surface wetting or providing of gloss. Polyolefin waxes are mainly used during the production or conversion processes of raw materials, semi-finished or finished products. According to the application, the property profile of polyolefin waxes must be adjusted in order to fulfil the various requirements. Some applications are mentioned in the following list. This list is only given to provide some examples, but is not intended to be exhaustive.

• In masterbatches or concentrates of additives, pigments, fragrances, etc., polyolefin waxes work as carrier and as aids to obtain better dispersion of pigments or additives. This provides a more homogenous distribution in the polymer after the consecutive conversion process. The viscosity of the additive concentrate at a given processing temperature must be coordinated with the viscosity of the polymer melt in which the concentrate is diluted. Usually, better distribution of pigments or additives of the masterbatch in the final polymer is obtained, if the melt viscosity of the concentrate is lower than that of the polymer.

• In inks and paints, polyolefin waxes serve as matting agents and also enhance the attrition or scratch resistance of the surface - especially at higher temperature - with clear advantages for the use or storage. The polyolefin waxes improve also the water barrier properties in certain cases. Furthermore, polyolefin waxes can improve water repellency, modify the surface appearance and reduce dirt collection on the surface.

• Polyolefin waxes are used as processing aids for polymers, whereby the melt flow is improved and the sticking of the polymer melts onto metal surfaces is reduced.

• Polyolefin waxes are also used as release agents for the injection molding or compression molding of parts made of plastics (thermoplastics, thermosets or elastomers). In order to function optimally as a release agent, the polyolefin wax must form a separating layer between the mold and the molded part. And to make sure that the release agent will not drip off from curves or angle faces of the mold, the polyolefin wax must provide optimal flow behaviour at the application temperature.

• A release agent function of polyolefin waxes similar to the one of mentioned above is known for wood particle board, which for example is used later in furniture building. • A release agent function is also needed for paper copier technology. During fixation, polyolefin waxes serve as release agents to ensure that the entire image is transferred to the paper. • Polyolefin waxes are also one of the main components of polishes, including heat- resistant polishes, used for wood surfaces, floors, fabrics, leather or lacked objects including car bodyworks. They provide surface protection and gloss. In certain cases, higher working temperatures are achieved by using polyolefin waxes with higher drop points. • Polyolefin waxes are used to increase the softening point of hydrocarbon (paraffin) waxes, for instance to achieve higher temperature resistance of care product pastes. In such cases, the polyolefin wax is blended to the hydrocarbon wax.

• Adhesives systems, especially hot melt adhesive systems, contain polyolefin waxes to regulate the flow behaviour or are even completely based on polyolefin waxes, for example on chemically modified polypropylene base. Polyolefin waxes with adjusted drop point help to limit or to avoid dripping and improve the working temperature of such adhesive systems. Furthermore, polyolefin waxes, especially in micronized form, are used as agents to avoid clumping of the hotmelt adhesive granulate or powder during transport or storage. • A further application for polyolefin waxes is their use as additives to improve the thermal resistance of traffic lane paints against deformation during the exposure to sun and vehicles.

• Specific polar polyolefin waxes, especially grafted-polypropylene waxes, are used as coupling agents in blends of incompatible polymers, i.e. enhancement of phase compatibility and thus of the physical properties of the blended polymers.

• Polyolefin waxes can be used as lubricants in metal working fluids, because they form a lubricating film between the mold, usually metallic, and the processed article. In order to function optimally as a release agent, the polyolefin wax must be solid when used and / or must form a separation layer. Afterwards, easy wash out without leaving residues on the surface of the mold or of the processed article is required. The similar function is also employed in ceramic processing.

• Lubrication of needles can be achieved with polyolefin waxes. Due to the high friction occurring during operations such as stitching or sewing, polyolefin waxes with high melting point are usually more suitable to ensure high speed and long needle life. • Polyolefin waxes can also form films, when used as suspension. They can form a permanent layer, applied or sprayed onto the surface of plants or fruits. As a consequence, for example a pesticide can enter quicker into the plant or another pesticide remains longer on the plant surface, which in both cases extend their effectiveness.

Another consequence of the waxy film formation is the limited drying out and the preservation of the surface from abrasion marks.

• Polyolefin waxes are components in candles. Here, polyolefin waxes modify the melting temperature and serve as modifier for the production of various candle grades. These grades are then distinguished in heat resistance, defined dripping behavior, better adjusted gloss or ductility.

• Related to candles, increase of flexibility and of drop point is advantageous for polyolefine wax sculpture (ceroplastic compounds).

• Chewing gum consistency can be adjusted by polyolefin waxes. In this application, the migration features and innocuity of polyolefin waxes are of paramount importance.

• Polyolefin waxes are used to coat paper employed in the production of disposable plates or cups and are also ideally suited for coating frozen food containers. Polyolefin waxes can be employed in wallpapers and in decorative paper for surface finishing and smoothing. Paper is laminated with polyolefin wax to avoid the migration of fat from foodstuff into and through the paper.

• Polyolefin waxes can serve to regulate the rheology of carbon paper masses, on both paper sides (pigment side and reverse side).

• Uses in the construction industry and road work are also typical for polar polyolefin waxes, for instance as bitumen modifiers for regulation of the thermal properties at elevated temperatures of bitumen. Another example is the use as release agent forming a separating layer for high-quality concrete work.

• In the cosmetic and pharmaceutical industry, polyolefin waxes and related products have varied applications. Polyolefin waxes provide tackiness, give consistency, and act as film builder, emollient, carrier, hydrophobing agent, thickening agent or binder for powders. Important applications for polyolefin waxes in the cosmetic industry are oil-in-water and water-in-oil formulations e.g. for creams and lotions. Solid polyolefin waxes are used in lipsticks and depilatory waxes.

• Polyolefin waxes are employed for corrosion protection of various metals. Here, they can also be employed as blends together with synthetic polymers and resins and / or combined with anti-corrosion agents. After spraying, they form a waxy film, which protects • from corrosion and scratches. In metal processing, the protection is against the attack of cutting fluid or drawing oils and greases. Further typical application areas include the automotive industry and the extensive lubricant sector. Dispersed polyolefin waxes are required for temporary corrosion protection e.g. for cars, machines or equipment during transportation. After use, the waxy layer can be removed from the originally shining surface.

• In rubber and tires, polyolefin waxes (however rather paraffin waxes), due to their flexibility and migration properties, provide sustainable surface protection and act also as compatibilizer for the different ingredients.

• Phase change materials, which are used for temperature control, can be based on microcapsules filled with polyolefin wax. The adjustment of the softening point of the wax enables fine-tuning of the thermal features (phase change temperature, leaking rate ...) of phase change materials. • Polar polyolefin waxes are used as modifiers for fillers, since wax-coated fillers exhibit lower absorption behavior and get better dispersed in the matrix, in which they are used, due to the improved compatibility provided by the wax.

• Polyolefin waxes of higher temperature resistance serve as lubricant for metallic wire drawing. In this metal processing, adjustment of drop points or softening points respectively is of industrial relevance for the achievement of efficient lubrication under high processing speed, high temperature and wider service conditions.

• Polyolefin waxes can be used as lubricants in sewing, stretching and thickening of yarns for knitted and woven goods. Higher temperatures are often requested in this application.

• Polyolefin waxes are applied to fabrics for example for higher gloss. A higher drop point or softening point respectively provides improved washfastness.

More specifically, the modification of the softening behaviour of polyolefin waxes according to this invention are especially important for the following enumerated applications using said modified waxes or the articles originating from these applications respectively:

• in printing inks and paints

• in injection molding or compression molding of parts made of plastics like thermoplastics, thermosets or elastomers

• in hot melt adhesive systems • in hot melt adhesive granulate or powders during transport or storage • in polishes, including heat-resistant polishes, used for wood surfaces, floors, fabrics, leather or lacked objects

• in traffic lane paints • in candles

• in bitumen

• in cosmetics

• in wax-filled microcapsules of phase change materials

• in auxiliaries for metallic wire drawing • in lubricants for sewing, stretching and thickening of yarns

The invention can advantageously being applied by the use of polyolefin waxes modified in their thermal softening behaviour according to this invention as additives in inks and paints, in injection molding of plastic, in compression molding of plastic, in hot melt adhesives, in candles, in bitumen, in cosmetics, in microcapsules of phase change materials, in lubricants for metal wire drawing and in lubricants for yarns.

A further aspect of this invention is the use of polyolefin waxes modified in their thermal softening behaviour according to this invention as additives in inks and paints, in injection molding of plastic, in compression molding of plastic, in hot melt adhesives, in candles, in bitumen, in cosmetics, in microcapsules of phase change materials, in lubricants for metal wire drawing and in lubricants for yarns, wherein all of these articles are free of a polyolefin other than a polyolefin wax.

This invention relates also to articles, which are free of a polyolefin other than a polyolefin wax, and which contain a polyolefin wax, which is modified in its thermal softening behaviour by incorporation of at least one compound of formula I.

A further aspect of this invention is the use of at least one compound of formula I for modifying the thermal softening behaviour of a polyolefin wax.

A still further aspect of this invention is a compostion containing a polyolefin wax and at least one compound according to formula I which is free of a polyolefin other than a polyolefin wax. Polyolefins which are not polyolefin waxes are preferably understood as having an average molecular weight (Mw) higher than 50000 g/mol.

The compounds of formula I are partly known and partly new.

The following compounds are a further aspect of this invention: 1 ,3,5-tris-(3-methylbutyrylamino)benzene

- 1 ,3,5-tris-(2-methylbutyrylamino)benzene

- 1 ,3,5-tris-(2-methylpentanoylamino)benzene

- 1 ,3,5-benzenetricarboxylic acid tris-[(2-methylbutyl)amide]

- 1 ,3,5-benzenetricarboxylic acid tris-[(1 -propylbutyl)amide].

Several compounds of formula I are disclosed for example in US-B-7235191 , US-B-7423088 and US-A-2007/0149663.

The compound 1 ,3,5-cyclohexanetricarboxylic acid tris-[(1 ,1 ,3,3-tetramethylbutyl)amide] is e.g. described in Tetrahedron Letters, Vol. 36, No. 18, pp. 3255-3258 (1995) by C. Raposo et al.

The compounds 1 ,3,5-tris[acetylamino]benzene and 1 ,3,5-tris(propionylamino)benzene are e.g. described in Chemische Berichte, 103, 200-204 (1970) by H. Stetter et al.

The compound 1 ,3,5-tris[2,3-dihydroxybenzoylamino]benzene is e.g. described in Journal of the American Chemical Society, 123, 8923-8938 (2001 ) by D. L. Caulder et al.

The compounds of formula I can be prepared by methods known in the art. Some of them are disclosed for example in the above mentioned references. They can also be prepared for example without the use of a solvent. Other compounds may be prepared in analogy to the methods disclosed in the above mentioned references.

A general example of the preparation of the compounds of the formula (I) in case of 1 ,3,5- tris[carbonylamino]benzene derivatives with three times the same substitutent is as following: The compounds of formula (I) can be synthesized e.g. by hydrogenation of 1 ,3,5- trinitrobenzene, 3,5-dinitroaniline or 1 ,3-diamino-5-nitrobenzene with hydrogen and an appropriate metal catalyst in an appropriate organic solvent. The thus obtained 1 ,3,5- triaminobenzene can be isolated or optionally transferred into the corresponding hydrochloride and can be purified in both forms by recrystallization from an appropriate solvent. It is also possible to use the solution of the crude trisamine or the isolated crude trisamine (with or without removal of the water formed in the hydrogenation) for the subsequent acylation reaction. Possible catalysts are e.g. Pd, PtO₂, Raney-Nickel etc., preferably the commercially available versions on carbon support. The hydrogenation can be carried out under normal pressure or under pressure at temperatures between 20 and 120 ⁰C (Safety checks are highly recommended before scale up). Appropriate solvents for the hydrogenation are e.g. tetrahydrofuran (THF), THF / methanol, dimethylformamide (DMF) or N-methylpyrrolidinone (NMP). An alternative procedure is reduction with Raney-Nickel and

hydrazine as hydrogen source (see e.g. Organikum, chapter 8.1 , Reduktion von

Nitroverbindungen und Nitrosoverbindung, Berlin, 1970) or other known standard reductions. Recrystallization can be carried out e.g. with methanol, ethanol or other alcohols. The free amine (or the amine obtained from the hydrochloride and an appropriate base) can be acylated with a stoichiometric amount or an excess of the corresponding carbonyl chloride, preferably in the presence of an organic or inorganic non-interacting base e.g. triethylamine, tributylamine, pyridine; another method uses a stoichiometric amount or an excess of the anhydride of the carboxylic acid as acylating agent; in this case no base is required. The reaction is carried out in the absence or preferably in the presence of a solvent. The ideal reaction temperature depends on the nature of the acylating agents (e.g. 0° -100⁰C). Isolation / purification of the final product is carried out by precipitation / recrystallization / washing with an appropriate mixture of water / organic solvent or organic solvent / organic solvent or with a pure solvent, e.g. DMF / water, NMP / water, methanol, ethanol, acetone, ethyl acetate, toluene, cyclohexane, hexane etc. Furthermore, chromatography with organic solvents or mixtures thereof or with water as mentioned above can be employed for isolation / purification.

The preparation of the compounds of the formula (I) in case of 1 ,3,5- tricarbonylaminobenzene derivatives with two different substitutents can be conducted as outlined in US-A-2007/0149663, pages 24-28. For example, the respective 3,5-dinitro- carbonylaminobenzene derivative is hydrogenated to the respective 3,5-diamino- carbonylaminobenzene derivative. Acetylation with the respective carbonyl chloride or carboxylic acid anhydride derivative yields the respective 1 ,3,5-tricarbonylaminobenzene derivative.

The preparation of the compounds of the formula (I) in case of 3,5-dicarbonylaminobenzene carboxylic acid amide derivatives can be conducted as outlined in US-A-2007/0149663, pages 28-37. For example, 3,5-dinitrobenzoyl chloride is reacted with the respective amine and afterwards this respective 3,5-dinitrobenzene carboxylic acid amide derivative is hydrogenated to the respective 3,5-diaminobenzene carboxylic acid amide derivative. Acetylation with the respecitive carbonyl chloride or carboxylic acid anhydride yields the respective 3,5-dicarbonylaminobenzene carboxylic acid amide derivative.

The preparation of the compounds of the formula (I) in case of 5-carbonylaminobenzene-1 ,3- dicarboxylic acid bisamide derivatives can be conducted as outlined in US-A-2007/0149663,

pages 37-43. For example, 5-nitrobenzene-1 ,3-dicarboxylic acid dichloride is reacted with the respective amine and afterwards, this respective 5-nitrobenzene-1 ,3-dicarboxylic acid bisamide is hydrogenated towards the respective 5-aminobenzene-1 ,3-dicarboxylic acid bisamide derivative. Acetylation with the respective carbonyl chloride or carboxylic acid anhydride yields the respective 5-carbonylaminobenzene-1 ,3-dicarboxylic acid bisamide derivative.

A general example of the preparation of the compounds of the formula (I) in case of tricarboxylic acid trisamide derivatives with three times the same substituent is as following: The compounds of the formula (I) can be prepared in analogy to known processes, for example by reacting an appropriate amine with the respective tricarbonyl trichloride precursor as described for example in the standard works such as Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], published by Georg Thieme, Stuttgart, under reaction conditions which are known. In carrying out these reactions, it is also possible to take advantage of variants known per se which are not specifically mentioned here. The starting substances can, if so desired also be formed in situ, by not isolating them out of the reaction mixture but immediately reacting them further to the compounds of the formula (I).

Examples

Preparation of 1 ,3,5-triaminobenzene 8 g (0,044 mol) 3,5-dinitroaniline are dissolved in 400 ml tetrahydrofuran and 50 ml methanol. This solution is hydrogenated in a laboratory autoclave (Buechi) by addition of 1.6 g Pd/C (10% Pd) as catalyst and stirring for 12 h under a hydrogen pressure of 3.5 bar at 35°C. Afterwards, the solution is filtrated with the aid of Alox N under argon and the solvent mixture is removed from the filtrate in vacuum. The crude material is dried under high vacuum and used without further purification in the subsequent synthesis. Yield: 5.30 g (0.044mol / 98% of theory) Characterisation: 1H-NMR (DMSOd₆): δ [ppm] = 4,30 (s, 6H, NH); 5,13 (s, 3H, CH)

General procedure for acyl chloride precursors

^Rγ°

Cl

Dichloromethane and the respective carboxylic acid are put under argon in a Schlenk flask. Oxalyl chloride is slowly added at 0⁰C under stirring and cooling with ice. Afterwards, the reaction mixture is stirred at 50⁰C external oil bath temperature for 12h. Then, excessive oxalyl chloride and solvent are removed in vacuum. The crude material is employed without further purification in the subsequent synthesis.

General procedure for prepartion of 1 ,3,5-tris(aminocarbonyl)benzene derivatives N-methylpyrrolidone (NMP), pyridine, lithium chloride and 1 ,3,5-trisaminobenzene are put in a Schlenk flask under argon. The respective acyl chloride is slowly added at 0⁰C under stirring and cooling with ice. Afterwards, the reaction mixture is stirred at 80⁰C external oil bath temperature for 2h. After cooling, the reaction mass is dropped into the 5-fold amount of ice water and kept over night. After filtration, the crude material is dried under high vacuum and purified by recrystallisation from organic solvents or by column chromatography. Example 1 : 1 ,3 ,5-tris-(3-methylbutyrylamino)benzene

-1 A -1 \

batch: 1.50 g (0.012 mol) 1 ,3,5-tιϊaminobenzene, 4.89 g (0.040 mol) 3-methylbutyryl chloride,

80 ml NMP, 20 ml pyridine, 0,1 g LiCI purification: column chromatography (cyclohexane / ethyl acetate 1 : 1 ), precipitation from methanol with hexane yield: 0.66 g (0,002 mol / 15% of theory) mp_: 210°C.

MS (70 eV): 375 (M⁺).

Example 2: 1 ,3 ,5-tris-(2-methylbutyrylamino)benzene

(compound 102) batch: 0.86 g (0.007 mol) 1 ,3,5-triaminobenzene, 2.89 g (0.024 mol) 2-methylbutyryl chloride, 70 ml NMP, 15 ml pyridine, 0.1 g LiCI purification: recrystallisation from cyclohexane / ethanol yield: 1.82 g (0.005 mol / 69% of theory) mp_: 301 °C.

MS (70 eV): 375 (M⁺).

Example 3: 1 ,3,5-tris-(2-methylpentanoylamino)benzene

(compound 103) batch: 0.86 g (0.007 mol) 1 ,3,5-tιϊaminobenzene, 3.23 g (0.024 mol) 2-methylpentanoyl chloride, 70 ml NMP, 15 ml pyridine, 0,1 g LiCI purification: recrystallisation from toluene and afterwards from cyclohexane / ethyl acetate yield: 1.10 g (0.003 mol / 38% of theory) mp_: 313°C

MS (7O eV): 417 (M⁺).

Example 4: 1 ,3,5-tris-(2 ,2-dimethylpropionylamino)benzene

(compound 104)

batch: 4.65 g (0.02 mol) 1 ,3,5-triaminobenzene, 9.42 g (0.07 mol) 2,2-dimethylpropionyl chloride, 250 ml NMP, 50 ml pyridine, 0,5 g LiCI purification: warming in hexane and afterwards column chromatography (hexane / tetrahydrofurane 2:1 ) yield: 3.86 g (0.009 mol / 46% of theory) mp_: 313°C

MS (7O eV): 417 (M⁺).

General procedure for preparation of 1 ,3,5-benzentricarboxylic acid trisamide derivatives N-methylpyrrolidone (NMP), pyridine, lithium chloride and the respective amine are put in a Schlenk flask under argon. 1 ,3,5-benzenetricarbonyl trichloride is slowly added at 0⁰C under stirring and cooling with ice. Afterwards, the reaction mixture is stirred at 80⁰C external oil bath temperature for 2h. After cooling, the reaction mass is dropped into the 5-fold amount of ice water and kept over night. After filtration, the crude material is dried under high vacuum and purified by recrystallisation from organic solvents. Example 5: 1 ,3,5-benzenetricarboxylic acid tris-(n-butylamide)

(compound 105) batch: 8.00 g (0.030 mol) 1 ,3,5-benzentricarbonyl trichloride, 7.35 g (0.100 mol) n- butylamine, 250 ml NMP, 50 ml pyridine, 0,1 g LiCI purification: 2-fold crystallization from acetone yield: 4.40 g (0.012 mol / 40% of theory) rnp_: 239°C MS (70 eV): 375 (M⁺).

Example 6: 1 ,3,5-benzenetricarboxylic acid tris-[(3-methylbutyl)amide]

(compound 106) batch: 2.65 g (0.010 mol) 1 ,3,5-benzentricarbonyl trichloride, 2.88 g (0.033 mol) 3- methylbutylamine, 70 ml NMP, 15 ml pyridine, 0,1 g LiCI purification: recrystallization from acetone yield: 3.00 g (0.007 mol / 72% of theory) rnp_: 263°C MS (7O eV): 417 (M⁺).

Example 7 1 ,3,5-benzenetricarboxylic acid tris-[(2-methylbutyl)amide]

(compound 107) batch: 1.44 g (0.005 mol) 1 ,3,5-benzenetricarbonyl trichloride, 1.33 g (0.015 mol) 2- methylbutylamine, 40 ml NMP, 10 ml pyridine, 0,1 g LiCI purification: recrystallization from ethyl acetate yield: 1.38 g (0.003 mol / 62% of theory) mp_: 317°C MS (7O eV): 417 (M⁺).

Example 8: 1 ,3,5-benzenetricarboxylic acid tris-[(1-propylbutyl)amide]

(compound 108) batch: 2.81 g (0.01 1 mol) 1 ,3,5-benzenetricarbonyl trichloride, 4.00 g (0.035 mol) 1- propylamine, 150 ml NMP, 30 ml pyridine, 0,1 g LiCI purification: recrystallization from toluene and afterwards from methanol yield: 2.1 1 g (0.004 mol / 38% of theory)

MS (70 eV): 501 (M⁺).

Example 9: 1 ,3,5-benzenetricarboxylic acid tris-[(1 ,1 ,3,3-tetramethylbutyl)amide]

(compound 109) batch: 13.3 g (0.05 mol) 1 ,3,5-benzentricarbonyl trichloride, 24.6 g (0.19 mol) 1 ,1 ,3,3- tetramethylbutylamine, 300 ml NMP, 80 ml pyridine, 0,3 g LiCI purification: recrystallization from N,N-dimethylformamide yield: 20.84 g (0.004 mol / 77% of theory) mp_: 315°C

MS (70 eV): 544 (M⁺). Example 10: cis,cis-1 ,3,5-cyclohexanetricarboxylic acid tris-[(1 ,1 ,3,3-tetramethylbutyl)amide]

(compound 1 10) batch: 4.8 g (0.018 mol) cis, cis-1 ,3,5-cyclohexanetricarbonyl trichloride (synthesized from cis,cis-1 ,3,5-cyclohexanetricarboxylic acid of 98% purity), 7.5 g (0.058 mol) 1 ,1 ,3,3- tetramethylbutylamine, 150 ml NMP, 30 ml pyridine, 0.2g LiCI purification: recrystallization from acetone yjejd: 6.81 g (0.012 mol / 70% of theory) mp: 355°C MS (70 eV): 550 (M+).

Example 11

Materials

For the following examples, a polyethylene wax and several polypropylene waxes were used. The polyethylene wax is Licowax^® PE520 (RTM, Clariant), which is produced according to the Ziegler-Natta low pressure process with a molecular weight of around 2000, and received as pellets.

The polypropylene waxes are Licocene^® PP 1502 (RTM, Clariant), Licocene^® PP 1602

(RTM, Clariant) and Licocene^® PP 2602 (RTM, Clariant). All three are produced with a metallocene catalyst and received in powder form.

The waxes were used in the form in which they are received.

Preparation of the modified on polvolefin waxes

The additive is added in an amount of 0.04% based on the weight of the wax. The powder- powder or powder-pellet mix is then melted at 200⁰C during 5 minutes. The melt gets thoroughly homogenized with an Ultra-Turrax T25 mixer (Jahnke und Kunkel, IKA) during 30 seconds at 200⁰C. The melt is then put into the drop point crucible or softening point crucible respectively, in which the samples are first annealed at 200⁰C during 2 minutes and then cooled at a controlled rate of 20 °C/min (whereby the opening of the nipple is closed with an aluminum foil). The drop point or softening point is then determined on these samples. Determination of the drop point and softening point

The drop point or the softening point respectively of the pure polyolefin waxes and the versions thereof with additives were measured with a Mettler Toledo FP83 HT apparatus. The measurement of the samples prepared as described above was started at a temperature 15°C below the drop point or the softening point respectively of the pure polyolefin wax. The drop point or the softening point respectively are defined as the temperature at which, upon heating at 2 °C/min, the first drop or a 20 mm long melt respectively appears below the opening of the nipple (of 2.8 mm or 6.35 mm diameter respectively) as described in standards ASTM D3954-94 (2004) or ASTM D3104-99 (1995) respectively. Due to the different melt viscosities and drop shaping features of the tested products, the drop points of the polyethlene-based waxes (pure and versions with additives) of Licowax^® PE 520 or the softening point respectively of the polypropylene-based waxes Licocene^® PP 1502, PP 1602 and PP 2602 (pure and version with additives) respectively were measured. The stated drop point or the softening point respectively is the average value of three measurements. The results are listed in tables 1 and 2 below.

Table 1

Table 2

Claims

Claims:

1. A method for modifying the thermal softening behaviour of a polyolefin wax, which comprises the incorporation into the wax of at least one compound of the formula (I)

X₁ y^/Q^y ^{(l )}

R₃^ ^{3 2^}R₂ wherein

Q is a C₃-Ci₂alkyltriyl, a C₃-Ci₂alkenyltriyl, a tris(Ci-C₈alkylene)amine, a C₃-Ci₂cycloalkyltriyl or is

of , t.,he f ,ormu .la

, or ;

Xi, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO-O-, -O-CO-NH-, - NH-CO-, -CO-NH, -COO- or -O-; Ri, R₂ and R₃ are independently from each other Ci-C₂oalkyl unsubstituted or substituted by one or more hydroxyl or halogen,

C₂-C₂₀alkenyl unsubstituted or substituted by one or more hydroxyl or halogen,

C₃-C₂₀alkinyl,

C₂-C₂₀alkyl interrupted by oxygen or sulfur,

C₃-Ci₂cycloalkyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, (C₃-Ci₂cycloalkyl)-Ci-Ci₀alkyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, bis[C₃-Ci₂cycloalkyl]-Ci-Ci₀alkyl unsubstituted or substituted by one or more d-

C₂₀alkyl, a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C₂₀alkyl, phenyl unsubstituted or substituted by one or more radicals selected from CrC₂₀alkyl,

Ci-C₂₀alkoxy, Ci-C₂₀alkylamino, di(Ci-C₂₀alkyl)amino, hydroxy, nitro, halogen or d-

Cβhaloalkyl, phenyl-Ci-C₂oalkyl unsubstituted or substituted by one or more radicals selected from

Ci-C₂₀alkyl, C₃-Ci₂cycloalkyl, phenyl, CrC₂₀alkoxy, hydroxy, halogen or CrC₈haloalkyl, phenylethenyl unsubstituted or substituted by one or more Ci-C₂₀alkyl, phenyloxymethyl unsubstituted or substituted by one or more CrC₂oalkyl, biphenyl-(Ci-Ci_Oalkyl) substituted by one or more Ci-C₂oalkyl, naphthyl unsubstituted or substituted by one or more Ci-C₂oalkyl, naphthyl-CrC₂oalkyl unsubstituted or substituted by one or more Ci-C₂oalkyl, naphthyloxymethyl unsubstituted or substituted by one or more CrC₂₀alkyl, biphenylenyl, fluorenyl, anthryl,

5- to 6-membered heterocyclic radical unsubstituted or substituted by one or more C_r

C₂₀alkyl, or tri-(Ci-Cioalkyl)-silyl-(Ci-Ci_Oalkyl).

2. A method according to claim 1 wherein

Q is of the formula or X₁, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO-O, -O-CO-N-, NH-

CO- or -CO-NH-;

Ri, R₂ and R₃ are independently from each other

Ci-Ci₂alkyl unsubstituted or substituted by 1 , 2 or 3 hydroxy or halogen, C₂-C₂₀alkenyl unsubstituted or substituted by 1 , 2 or 3 hydroxy or halogen, C₂-Ci₀alkyl interrupted by oxygen,

C₃-C₆cycloalkyl unsubstituted or substituted by 1 , 2, 3 or 4 d-C₄alkyl, (C₃-C₆cycloalkyl)-Ci-Ci₀alkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl, bis-[C₃-C₆cycloalkyl]-Ci-Ci₀alkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl,

phenyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from CrC₄alkyl, d-

C₄alkoxy, Ci-C₄alkylamino, di-(Ci-C₄alkyl)-amino, hydroxyl, nitro, halogen and d-

C₄haloalkyl, phenyl-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from d-

C₄alkyl, C₃-C₆cycloalkyl, phenyl, Ci-C₄alkoxy, hydroxy, halogen and Ci-C₄haloalkyl, phenylethenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl, phenyloxymethyl unsubstituted or substituted by 1 ,2 or 3 Ci-C₄alkyl, biphenyl-(Ci-Ci_Oalkyl) substituted by 1 , 2 or 3 d-C₄alkyl, naphthyl unsubstituted or substituted by 1 , 2 or 3 d-dalkyl, naphthyl-d-doalkyl unsubstituted or substituted by 1 , 2 or 3 d-dalkyl, naphthyloxymethyl unsubstituted or substituted by 1 , 2 or 3 d-dalkyl, biphenylenyl, fluorenyl, anthryl,

3-pyridinyl, 4-pyridinyl, 2-hydroxypyridin-3-yl, 2-furyl, 3-furyl, 1-methyl-2-pyrrolyl, or tri-(d-do)alkyl-silyl-(d-d_oalkyl).

3. A method according to claims 1 to 2 wherein

Q is of the formula or

Xi, X₂ and X₃ are independently from each other -NH-CO-NH-, -NH-CO- or -CO-NH-;

Ri, R₂ and R₃ are independently from each other

C₃-Ci₂alkyl,

C₃-Ci₀alkyl interrupted by oxygen,

C₃-C₆cycloalkyl unsubstituted or substituted by 1 , 2, 3 or 4 d-C₄alkyl,

(C₃-C₆cycloalkyl)-Ci-Ci₀alkyl unsubstituted or substituted by 1 , 2 or 3 d-C₄alkyl, phenyl unsubstituted or substituted by 1 , 2 or 3 d-C₄alkyl, phenyl-Ci-Cioalkyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from d-

C₄alkyl and CrC₄alkoxy, biphenyl-(Ci-Ci_Oalkyl), naphthyl-Ci-Cioalkyl, or tri-(Ci-Ci₀alkyl)-silyl-(Ci-C₅)alkyl.

4. A method according to claims 1 to 3 wherein

Q is of the formula or

Xi, X₂ and X3 are independently from each other -NH-CO- or -CO-NH-; Ri, R₂ and R₃ are independently from each other C₃-Ci₂alkyl.

5. A method according to claims 1 to 4 wherein

Q is of the formula or

Xi, X₂ and X₃ are -NH-CO-; Ri, R₂ and R₃ are the same C₃-Ci₂alkyl.

6. A method according to claims 1 to 4 wherein

Q is of the formula or

Xi, X₂ and X₃ are -CO-NH-;

Ri, R₂ and R₃ are the same C₃-Ci₂alkyl.

7. A method according to claim 1 to 4 and 6 wherein

Q is of the formula Xi, X₂ and X₃ are -CO-NH-;

Ri, R₂ and R₃ are the same C₃-Ci₂alkyl.

8. A method according to claims 1 to 7 wherein the overall concentration of one or more compounds of formula I is from 0.005% to 3%.

9. A method according to claims 1 to 8 wherein the polyolefin wax comprises a polyethylene, a polyethylene-based, a polypropylene or a polypropylene-based wax.

10. A method according to claims 1 to 9 wherein the thermal softening behaviour of the polyolefin wax is modified as confirmed by an enhancement of the drop point or an enhancement of the softening point respectively.

11. A method according to claim 10 wherein the enhancement of the drop point or the softening point respectively is more than 5°C but less than 90⁰C compared to the value of the same polyolefin wax without incorporation of at least one compound of formula I.

12. A method according to claims 1 to 11 wherein at least one compound of formula I is homogenously incorporated into the polyolefin wax which is in the liquid state.

13. A composition containing a polyolefin wax and a compound of formula I as defined in claims 1 to 7, which is free of a polyolefin other than a polyolefin wax.

14. The use of at least one compound of formula I as defined in claims 1 to 7 for modifying the thermal softening behaviour of a polyolefin wax.

15. The compounds

1 ,3,5-tris-(3-methylbutyrylamino)benzene, 1 ,3,5-tris-(2-methylbutyrylamino)benzene, 1 ,3,5-tris-(2-methylpentanoylamino)benzene,

1 ,3,5-benzenetricarboxylic acid tris-[(2-methylbutyl)amide] or

1 ,3,5-benzenetricarboxylic acid tris-[(1-propylbutyl)amide].