WO2010069854A2 - Cires de polyoléfine modifiées - Google Patents

Cires de polyoléfine modifiées Download PDF

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WO2010069854A2
WO2010069854A2 PCT/EP2009/066832 EP2009066832W WO2010069854A2 WO 2010069854 A2 WO2010069854 A2 WO 2010069854A2 EP 2009066832 W EP2009066832 W EP 2009066832W WO 2010069854 A2 WO2010069854 A2 WO 2010069854A2
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alkyl
substituted
unsubstituted
tert
formula
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WO2010069854A3 (fr
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Roman Kress
Hans-Werner Schmidt
Raphaël DABBOUS
Klaus Stoll
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
    • C07C233/42—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
    • C07C233/43—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of a saturated carbon skeleton
    • 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
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Definitions

  • the present invention relates to a method for the modification of the thermal softening behaviour of a polyolefin wax.
  • 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.
  • non-polar olefins e.g. ethylene or propylene
  • 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 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.
  • higher working temperatures without softening or dirt adhesion can be achieved by using polyolefin waxes with higher drop points or softening points respectively.
  • 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.
  • micronized polyolefin waxes or nanoparticle polyolefin waxes results in micronized polyolefin waxes or nanoparticle polyolefin waxes.
  • 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.
  • 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) R 1 X 1
  • Q is a C 3 -Ci 2 alkyltriyl, a C 3 -Ci 2 alkenyltriyl, a tris(Ci-C 8 alkylene)amine, a C 3 -Ci 2 cycloalkyltriyl or is
  • Xi, X 2 and X 3 are independently from each other -NH-CO-NH-, -NH-CO-O-, -O-CO-NH-, -
  • Ri, R 2 and R 3 are independently from each other
  • Ci-C 20 alkyl unsubstituted or substituted by one or more Ci-C 20 alkyl, (C 3 -Ci 2 cycloalkyl)-Ci-Ci 0 alkyl unsubstituted or substituted by one or more Ci-C 20 alkyl, bis[C 3 -Ci 2 cycloalkyl]-Ci-Ci 0 alkyl unsubstituted or substituted by one or more d-
  • C 20 alkyl a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 20 alkyl, phenyl unsubstituted or substituted by one or more radicals selected from CrC 20 alkyl, Ci-C 20 alkoxy, Ci-C 20 alkylamino, di(Ci-C 20 alkyl)amino, hydroxy, nitro, halogen or d-
  • Ci-C 20 alkyl C 3 -Ci 2 cycloalkyl, phenyl, CrC 20 alkoxy, hydroxy, halogen or CrC 8 haloalkyl, phenylethenyl unsubstituted or substituted by one or more Ci-C 20 alkyl, phenyloxymethyl unsubstituted or substituted by one or more Ci-C 20 alkyl, biphenyl-(Ci-Ci O alkyl) substituted by one or more Ci-C 20 alkyl, naphthyl unsubstituted or substituted by one or more Ci-C 20 alkyl, naphthyl-Ci-C 20 alkyl unsubstituted or substituted by one or more Ci-C 20 alkyl, naphthyl-Ci-C 20 alkyl unsubstituted or substituted by one or more Ci-C 20 alkyl, naphthyloxymethyl unsubstituted or substituted by one or more Ci-C
  • C 3 -C 12 alkyltriyl (preferably C 3 -C 6 alkyltriyl) is propane-1 ,2,3-triyl.
  • C 3 -Ci 2 alkenyltriyl (preferably C 3 -C 6 alkenyltriyl) is propene-1 ,2,3-triyl.
  • tris-(Ci-C8alkylene)amine examples include tris(methylene)amine, tris-(1 ,2-ethylene)amine, and tris-[1 ,2-(2-methyl)ethylene]amine.
  • C 3 -Ci 2 cycloalkyltriyl (preferably C 3 -C 6 cycloalkyltriyl, particularly C 5 - C ⁇ cylcoalkyltriyl) are cyclohexane-1 ,3,5-triyl and cyclohexane-1 ,2,4-triyl.
  • Ci-C 2 oalkyl e.g. branched C 3 -C 20 alkyl
  • 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-
  • C 2 -C 2 oalkenyl are C 2 -C 6 alkenyl and C 2 -C 4 alkenyl, 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.
  • C 3 -C 20 alkinyl are C 3 -Ci 8 alkinyl and C 3 -Ci 2 alkinyl.
  • 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.
  • C 2 -C 20 alkyl interrupted by oxygen are C 2 -C 20 alkyl 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.
  • C 2 -C 2 oalkyl interrupted by sulfur are numbers for sulfur and carbon atoms in analogy to the alkyl groups interrupted by oxygen atoms. Examples are (H 3 C) 3 C-S-CH 2 -, (H 3 C) 3 C-S-C 2 H 4 -, (H 3 C) 3 C-S-C 3 H 6 - and (H 3 C) 3 C-S-C 4 H 8 -.
  • C 3 -Ci 2 cycloalkyl are C 3 -C 6 cycloalkyl, particularly C 5 -C 6 cycloalkyl, which are unsubstituted or substituted by one or more, e.g. 1 , 2, 3 or 4, CrC 20 alkyl, preferably d- C 4 alkyl.
  • 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.
  • C 3 -Ci 2 cycloalkyl)-CrCi 0 alkyl are (C 3 -C 6 cycloalkyl, particularly C 5 -C 6 cycloalkyl)-Ci- Cio-(preferably Ci-C 4 )alkyl, which are unsubstituted or substituted by one or more, e.g. 1 , 2 or 3, Ci-C 20 alkyl, preferably Ci-C 4 alkyl.
  • Examples are cyclopentylmethyl, 2-cyclopentylethyl, cyclohexylmethyl, 2-cycohexylethyl, 3-cyclohexylpropyl, 4-cyclohexylbutyl and (4- methylcyclohexyl)methyl.
  • Preferred bis[C 3 -Ci 2 cycloalkyl]-CrCi 0 alkyl are bis(C 3 -C 6 cycloalkyl, particularly C 5 - C 6 cycloalkyl)-CrCio-(preferably Ci-C 4 )alkyl, which are unsubstituted or substituted by one or more, e.g. 1 , 2 or 3, Ci-C 20 alkyl, preferably Ci-C 4 alkyl.
  • An example is dicyclohexylmethyl.
  • Ci-C 20 alkyl examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C 4
  • phenyl unsubstituted or substituted by one or more radicals selected from d-C 2 oalkyl (preferably CrC 9 alkyl, particularly d-C 4 alkyl), Ci-C 2 oalkoxy (preferably Ci-C 4 alkoxy), Ci-C 2 oalkylamino (preferably Ci-C 6 alkylamino, particularly Ci-C 4 alkylamino), di(Ci-C 2 oalkyl)amino (preferably di(Ci-C 8 alkyl)amino, particularly di(Ci-C 4 alkyl)amino), hydroxy (preferably 1 to 2, particularly 1 ), nitro, halogen (preferably 1 to 2, particularly 1 ) or d-C 8 haloalkyl (preferably Ci-C 4 haloalkyl, particularly halomethyl) are phenyl, 3-methylphenyl, 3-methoxyphenyl, 4-methylphenyl, 4-ethyl
  • phenyl-Ci-C 20 alkyl (preferably phenyl-Ci-C 4 alkyl) unsubstituted or substituted by one or more radicals, e.g. 1 , 2 or 3 radicals, selected from CrC 20 alkyl (preferably CrC 9 alkyl, particularly Ci-C 4 alkyl), C 3 -Ci 2 cycloalkyl (preferably C 3 -C 6 cycloalkyl, particularly C 5 - C 6 cycloalkyl), phenyl, d-C 20 alkoxy (preferably Ci-C 4 alkoxy), hydroxy, halogen or d- C ⁇ haloalkyl (preferably Ci-C 4 haloalkyl, particularly halomethyl) are benzyl, ⁇ - cyclohexylbenzyl, diphenylmethyl, 1-phenylethyl, ⁇ -hydroxybenzyl, 2-phenylethyl, 2- phenylpropyl, 3-phenylpropyl,
  • phenylethenyl unsubstituted or substituted by one or more CrC 2 oalkyl e.g. 1 , 2 or 3 Ci-C 4 alkyl
  • 2-(4-methylphenyl)ethenyl is 2-(4-methylphenyl)ethenyl.
  • phenyloxymethyl unsubstituted or substituted by one or more Ci-C 20 alkyl e.g. 1 , 2 or 3 CrC 4 alkyl
  • phenoxymethyl and (4-methylphenoxy)methyl are phenoxymethyl and (4-methylphenoxy)methyl.
  • Examples of naphthyl unsubstituted or substituted by one or more Ci-C 2 oalkyl are 1 -naphthyl and 2-naphthyl.
  • naphthyl-CrC 2 oalkyl preferably naphthyl-Ci-C 9 alkyl, particularly naphthyl-d- C 4 alkyl
  • Ci-C 2 oalkyl e.g. 1 , 2 or 3 Ci-C 4 alkyl
  • naphthoxymethyl unsubstituted or substituted by one or more CrC 20 alkyl e.g. 1 , 2 or 3 CrC 4 alkyl
  • biphenylenyl, fluorenyl or anthryl examples 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-C 20 alkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are 3-pyridinyl, 4- pyridinyl, 2-hydroxypyridin-3-yl, 2-furyl, 3-furyl and 1-methyl-2-pyrrolyl.
  • halogen examples include fluorine atoms, chlorine atoms, bromine atoms and iodine atoms, preferably chlorine and fluorine atoms.
  • Ci-C 8 haloalkyl preferably Ci-C 4 haloalkyl, particularly halomethyl
  • Examples of a Ci-C 8 haloalkyl are dichloromethyl, difluoromethyl and trifluoromethyl.
  • Xi, X 2 and X 3 are independently from each other -NH-CO-NH-, -NH-CO-O, -O-CO-N-, NH-
  • R-i, R 2 and R 3 are independently from each other CrCi 2 alkyl unsubstituted or substituted by 1 , 2 or 3 hydroxy or halogen,
  • phenyl unsubstituted or substituted by 1 , 2 or 3 radicals selected from Ci-C 4 alkyl, d-
  • Ci-C 4 alkoxy biphenyl-(Ci-Ci O alkyl), naphthyl-Ci-Cioalkyl, or tri-(Ci-Ci 0 alkyl)-silyl-(Ci-C 5 )alkyl.
  • Xi, X 2 and X 3 are independently from each other -NH-CO- or -CO-NH-; Ri, R 2 and R 3 are independently from each other C 3 -Ci 2 alkyl.
  • Xi, X 2 and X 3 are -NH-CO-; Ri, R 2 and R 3 are the same C 3 -Ci 2 alkyl.
  • Xi, X 2 and X 3 are -NH-CO-;
  • Ri, R 2 and R 3 are the same and selected from 2-methylpropyl, 1-methylpropyl, 1-methylbutyl and 1 ,1-dimethylethyl.
  • Xi, X 2 and X 3 are -CO-NH-; Ri, R 2 and R 3 are the same C 3 -Ci 2 alkyl.
  • Q is of formula Xi, X 2 and X 3 are -CO-NH-;
  • Ri, R 2 and R 3 are the same and selected from n-butyl, 3-methylbutyl, 2-methylbutyl, 1- propylbutyl and 1 ,1 ,3,3-tetramethylbutyl.
  • Q is of the formula Xi, X 2 and X 3 are -CO-NH-; Ri, R 2 and R 3 are the same C 3 -Ci 2 alkyl.
  • Xi, X 2 and X 3 are -CO-NH-; R-i, R 2 and R 3 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.
  • 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-( ⁇ -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
  • 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.
  • 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.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • 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.
  • 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
  • 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-( ⁇ -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-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • 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.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
  • 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.
  • 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
  • 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.
  • esters of ⁇ -(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 -
  • esters of ⁇ -(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-triox
  • 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
  • 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
  • 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'-sec-but
  • azol-2-ylphenyl 2-[2'-hydroxy-3'-( ⁇ , ⁇ -dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-( ⁇ , ⁇ -dimethylbenzyl)phenyl]ben- zotriazole.
  • 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.
  • 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.
  • 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.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanol
  • 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-
  • 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, ⁇ -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(2,2,2,
  • 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.
  • 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.
  • 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 diphos
  • Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos ® 168, Ciba-Geigy), tris(nonylphenyl) phosphite,
  • 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.
  • 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
  • Thiosynergists for example dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers 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.
  • 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( ⁇ - dodecyl
  • Polyamide stabilisers for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.
  • inorganic substances for example talcum, metal oxides like titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals.
  • polymeric compounds for example ionic copolymers (ionomers), polyvinylcyclohexane, poly-(1 ,2-ethylene-1 ,3-cyclopentylene).
  • Nucleating agents based upon carboxy aluminum-hydroxide for example aluminum hydroxy-bis-[4-tert-butylbenzoate], commercially available as Sandostab 4030 (RTM).
  • 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).
  • 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.
  • the waxes of the present invention are non-polar or polar polyolefin waxes.
  • 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 400 0 C under nitrogen atmosphere.
  • polyolefin polymers e.g. LDPE, HDPE, i-PP
  • the direct polymerization of the monomers like for example ethylene or propylene, is employed at high scale and can be realized in two ways:
  • 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.
  • 1 -olefins examples include 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.
  • 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 ⁇ , ⁇ -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 C 3 -C 2 O-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.
  • 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.
  • 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.
  • 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. 10 0 C above the drop point) and with clear dripping can be measured by this method.
  • the softening point measurement 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 drop points or softening points respectively of polyolefin waxes are typically between 80 0 C and 170 0 C, 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.
  • the drop point or the softening point respectively of the polyolefin waxes ranges from 75°C to 215°C.
  • the melt viscosity - measured 10 0 C 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.
  • 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 90 0 C, particularly more than 10 0 C but less than 80°C, for example more than 20 0 C 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • the polyolefin wax 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.
  • the polyolefin wax 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.
  • 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.
  • Chewing gum consistency can be adjusted by polyolefin waxes.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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:
  • 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 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 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.
  • 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.
  • 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° -100 0 C).
  • 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.
  • chromatography with organic solvents or mixtures thereof or with water as mentioned above can be employed for isolation / purification.
  • 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).
  • a -1 ⁇ batch 1.50 g (0.012 mol) 1 ,3,5-t ⁇ aminobenzene, 4.89 g (0.040 mol) 3-methylbutyryl chloride,
  • Example 8 1 ,3,5-benzenetricarboxylic acid tris-[(1-propylbutyl)amide]
  • Example 9 1 ,3,5-benzenetricarboxylic acid tris-[(1 ,1 ,3,3-tetramethylbutyl)amide]
  • 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
  • Licocene ® PP 2602 (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.
  • 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 200 0 C during 5 minutes.
  • the melt gets thoroughly homogenized with an Ultra-Turrax T25 mixer (Jahnke und Kunkel, IKA) during 30 seconds at 200 0 C.
  • the melt is then put into the drop point crucible or softening point crucible respectively, in which the samples are first annealed at 200 0 C 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de modification du comportement de ramollissement thermique d'une cire de polyoléfine, lequel procédé comprend l'incorporation dans la cire d'au moins un composé représenté par la formule (I) dans laquelle Q est un groupe (alkyl en C3-C12)triyle, une tris(alkylène en C1-C8)amine, un groupe (cycloalkyl en C3-C12)triyle ou est représenté par la formule (II), ou X1, X2 et X3 représentent chacun indépendamment l’un de l’autre -NH-CO-NH-, -NH-CO-O-, -O-CO-NH-, -NH-CO-, -CO-NH, -COO- ou -O- ; R1, R2 et R3 sont divers radicaux aliphatiques ou aromatiques non substitués ou substitués.
PCT/EP2009/066832 2008-12-19 2009-12-10 Cires de polyoléfine modifiées WO2010069854A2 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10011617B2 (en) 2014-09-26 2018-07-03 The Chemours Company Fc, Llc Isocyanate derived organosilanes
CN112745241A (zh) * 2020-12-31 2021-05-04 中北大学 一种检测正己烷或环己烷的化合物及其制备方法
WO2021119632A1 (fr) * 2019-12-12 2021-06-17 Milliken & Company Composés trisamides et compositions les comprenant
WO2021119633A1 (fr) * 2019-12-12 2021-06-17 Milliken & Company Composés trisamides et compositions les comprenant
RU2797296C1 (ru) * 2019-12-12 2023-06-01 Милликен Энд Компани Трисамидные соединения и содержащие их композиции
US11773054B2 (en) 2020-12-14 2023-10-03 Milliken & Company Trisamide compounds and compositions comprising the same

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WO1997007158A1 (fr) * 1995-08-15 1997-02-27 Hoechst Celanese Corporation Cires ameliorees pour actionneurs
WO2002046300A2 (fr) * 2000-12-06 2002-06-13 Ciba Speciality Chemicals Holding Inc. Compositions en resine polypropylene
WO2004072168A2 (fr) * 2003-02-14 2004-08-26 Ciba Specialty Chemicals Holding Inc. Compositions de resine
US20040223987A1 (en) * 2000-12-13 2004-11-11 Veronique Ferrari Composition structured with a polymer containing a heteroatom and organogelator

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007158A1 (fr) * 1995-08-15 1997-02-27 Hoechst Celanese Corporation Cires ameliorees pour actionneurs
WO2002046300A2 (fr) * 2000-12-06 2002-06-13 Ciba Speciality Chemicals Holding Inc. Compositions en resine polypropylene
US20040223987A1 (en) * 2000-12-13 2004-11-11 Veronique Ferrari Composition structured with a polymer containing a heteroatom and organogelator
WO2004072168A2 (fr) * 2003-02-14 2004-08-26 Ciba Specialty Chemicals Holding Inc. Compositions de resine

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10011617B2 (en) 2014-09-26 2018-07-03 The Chemours Company Fc, Llc Isocyanate derived organosilanes
US11667603B2 (en) 2019-12-12 2023-06-06 Milliken & Company Trisamide compounds and compositions comprising the same
JP2023517423A (ja) * 2019-12-12 2023-04-26 ミリケン・アンド・カンパニー トリスアミド化合物およびトリスアミド化合物を含む組成物
US11724983B2 (en) 2019-12-12 2023-08-15 Milliken & Company Trisamide compounds and compositions comprising the same
CN115066413A (zh) * 2019-12-12 2022-09-16 美利肯公司 三酰胺化合物和包含所述三酰胺化合物的组合物
RU2802889C1 (ru) * 2019-12-12 2023-09-05 Милликен Энд Компани Трисамидные соединения и содержащие их композиции
JP2023517422A (ja) * 2019-12-12 2023-04-26 ミリケン・アンド・カンパニー トリスアミド化合物およびトリスアミド化合物を含む組成物
RU2797296C1 (ru) * 2019-12-12 2023-06-01 Милликен Энд Компани Трисамидные соединения и содержащие их композиции
EP4332088A3 (fr) * 2019-12-12 2024-05-15 Milliken & Company Composés trisamide et compositions les comprenant
WO2021119633A1 (fr) * 2019-12-12 2021-06-17 Milliken & Company Composés trisamides et compositions les comprenant
WO2021119632A1 (fr) * 2019-12-12 2021-06-17 Milliken & Company Composés trisamides et compositions les comprenant
EP4317128A3 (fr) * 2019-12-12 2024-04-10 Milliken & Company Composés trisamide et compositions les comprenant
CN115066413B (zh) * 2019-12-12 2024-01-09 美利肯公司 三酰胺化合物和包含所述三酰胺化合物的组合物
RU2811976C2 (ru) * 2019-12-12 2024-01-19 Милликен Энд Компани Трисамидные соединения и содержащие их композиции
JP7447270B2 (ja) 2019-12-12 2024-03-11 ミリケン・アンド・カンパニー トリスアミド化合物およびトリスアミド化合物を含む組成物
JP7447269B2 (ja) 2019-12-12 2024-03-11 ミリケン・アンド・カンパニー トリスアミド化合物およびトリスアミド化合物を含む組成物
US11773054B2 (en) 2020-12-14 2023-10-03 Milliken & Company Trisamide compounds and compositions comprising the same
CN112745241A (zh) * 2020-12-31 2021-05-04 中北大学 一种检测正己烷或环己烷的化合物及其制备方法

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