WO2000018833A1 - Melanges stabilisants synergiques - Google Patents

Melanges stabilisants synergiques Download PDF

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Publication number
WO2000018833A1
WO2000018833A1 PCT/EP1999/007092 EP9907092W WO0018833A1 WO 2000018833 A1 WO2000018833 A1 WO 2000018833A1 EP 9907092 W EP9907092 W EP 9907092W WO 0018833 A1 WO0018833 A1 WO 0018833A1
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group
groups
compound
butyl
general formula
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PCT/EP1999/007092
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English (en)
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Silvestro Costanzi
Carlo Neri
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Great Lakes Chemical (Europe) Gmbh
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Publication of WO2000018833A1 publication Critical patent/WO2000018833A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • C08K5/3435—Piperidines
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene

Definitions

  • the present invention relates to synergistic stabilizing mixtures.
  • the present invention relates to synergistic stabilizing mixtures comprising two specific polyalkylpiperidines with a high molecular weight and their use as heat, oxidative degradation and light stabilizers of organic polymers.
  • the present invention also relates to the polymeric compositions stabilized with the above synergistic mixtures and the end-articles obtained from said compositions.
  • Stabilizing mixtures comprising two polyalkylpiperidines are known in the art. For example, they are described in patents USA 4,692,486, USA 4,863,981 and USA 4,957,953, in International patent application WO 92/12201, in European patent applications EP 449,685 and EP 632,092, in English patent application GB 2,267,449 and in the publication ("Research Disclosure”) RD 34,549 (January 1993).
  • European patent EP 728,806 describes a stabilizing mix- ture comprising two specific polyalkylpiperidines one of which must be at least one compound having general formula (la) :
  • Ri is a C ⁇ -C ⁇ o alkyl group, a C 5 -C ⁇ 2 cycloalkyl group optionally substituted with C 1 -C 4 alkyl groups, a phenyl optionally substituted with C 1 -C 10 alkyl groups;
  • R 2 is a C 3 -C ⁇ o alkylene group;
  • R 3 is a hydrogen atom, a Ci-C ⁇ alkyl group, 0", a -CH 2 CN group, a C 3 -C 6 alkenyl group, a C 7 -C 9 phenylalkyl group optionally substituted in the phenyl radical with C ⁇ -C 4 alkyl groups, a Ci-C ⁇ acyl group; and
  • ni is a number ranging from 1 to 50 extremes included.
  • UVASIL 299 is a mixture of cyclic and linear products corresponding to general formula (la) described above: the quantity of cyclic products and linear products varies according to the molecular weight to be obtained.
  • the present invention therefore relates to stabilizing mixtures comprising at least one component (a) consisting of a compound having general formula (I) :
  • Ri represents a C ⁇ -C ⁇ 0 alkyl group; a C 5 -C ⁇ 2 cycloalkyl group, said cycloalkyl group optionally substituted with C1-C4 alkyl groups; a phenyl, said phenyl optionally substituted with C 1 -C 10 alkyl groups; R 2 represents a C 3 -C ⁇ 0 alkylene group;
  • R 3 represents a hydrogen atom; a Ci-Ca alkyl group; 0"; a -CH 2 CN group; a C 3 -C ⁇ alkenyl group; a C 7 -C 9 phenylal- kyl group, said phenylalkyl group optionally substituted in the phenyl radical with C 1 -C 4 alkyl groups; a Ci-Cs acyl group; n is a number ranging from 1 to 50 extremes included; and at least one component selected from the following polyalkylpiperidines (b) , (c) , (d) , (e) , (f) and (g) wherein:
  • (b) is at least one compound having general formula (II) :
  • R, R ⁇ , R 7 and R 8 each independently represent a hydrogen atom; a C ⁇ -C ⁇ 2 alkyl group; a Cs-C ⁇ 2 cycloalkyl group, said cycloalkyl group optionally substituted with C ⁇ -C alkyl groups; a phenyl group, said phenyl group optionally substituted with -OH groups and/or with Ci-Cio alkyl groups; a C 7 -C 9 phenylalkyl group, said phenylalkyl group optionally substituted in the phenyl group with -OH groups and/or Ci-Cio alkyl groups; a group having general formula (III) :
  • R 5 represents a C 2 -C ⁇ s alkylene group; a C 5 -C-7 cycloal- kylene group; a C 1 -C 4 alkylene-di (C 5 -C 7 -cycloalkylene) group; or the substituents R, R 5 and R 6 , together with the ni- trogen atoms to which they are bound, form a heterocy-rod ring with 5-10 atoms; or, R 7 and R 8 , together with the nitrogen atoms to which they are bound, form a heterocyclic ring with 5- 10 atoms; - R 9 has the same meanings as R 3 ; n 2 is a number ranging from 2 to 50 extremes included, and at least one of the radicals R 4 , Re, R and R 8 represents a group having general formula (III) ; (c) is at least one compound obtained by reacting a compound obtained by the reaction of a polyamine having general formula (IVa) with cyanuric chloride, with
  • n a , n b and n c are each independently a number ranging from 2 to 12 extremes included;
  • Rio represents a hydrogen atom; a C ⁇ -C ⁇ 2 alkyl group; a C 5 -C ⁇ 2 cycloalkyl group; a phenyl group; a C 7 -C 9 phenylalkyl group; Ru has the same meanings as R 3 ;
  • R ⁇ 2 represents a hydrogen atom or a methyl
  • Ri3 represents a direct bond or a C ⁇ -C ⁇ o alkylene group
  • n 4 is a number ranging from 2 to 50 extremes included
  • (e) is at least one compound having general formula (Via) or (VIb) :
  • n 5 and n 5 * are each independently a number ranging from 2 to 50 extremes included;
  • (f) is at least one compound having general formula (VII) :
  • R 14 and R i8 each independently represent a direct bond; or an -N (Xi) -CO-X 2 -CO-N (X 3 ) - group wherein Xi and X 3 , each independently represent a hydrogen atom, a C ⁇ -C 8 alkyl group, a C 5 -C ⁇ 2 cycloalkyl group, a phenyl group, a C-C 9 phenylalkyl group, a group having general formula (III) ; X 2 represents a direct bond, a C ⁇ -C 4 alkylene group;
  • Ri 5 has the same meanings as R 3 ; Ri 6 , R_ , R 20 and R 2i , each independently represent a hy- drogen atom; a C ⁇ -C 30 alkyl group; a C 5 -C ⁇ 2 cycloalkyl group; a phenyl group;
  • Ri 9 represents a hydrogen atom; a C 1 -C 30 alkyl group; a C 5 -C ⁇ 2 cycloalkyl group; a C 7 -C 9 phenylalkyl group; a phenyl group; a group having general formula (III); - n 6 is a number ranging from 1 to 50 extremes included; (g) is at least one compound having general- formula (VIII]
  • R 2 , R 23 , R 24 , R 5 and R 26 each independently represent a direct bond; a Ci-Cio alkylene group;
  • R 2 has the same meanings as R 3 ; n 7 is a number from 1 to 50 extremes included.
  • alkyl groups having up to 30 carbon atoms are: methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1- methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n- heptyl, isoheptyl, 1, 1, 3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1, 1, 3-trimethylhexyl,
  • R 3 , R , Rn, Ri 5/ R i7 , R 2 ⁇ and R 27 preferably represent a C 1 -C 4 alkyl group, in particular a methyl.
  • the substituents R 16 and R 20 preferably represent a C ⁇ -C 5 alkyl group, in particular a Ci 5 -C 25 alkyl group such as, for example, hexadecyl or a C ⁇ 8 - C 22 alkyl group.
  • the substituent Rig preferably represents a C ⁇ -C 25 alkyl group, in particular octadecyl.
  • C 5 -C ⁇ 2 cycloalkyl groups are: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, etc.
  • C 5 -C 8 cycloalkyl groups are preferred, in particular cyclohexyl.
  • C 5 -C ⁇ 2 cycloalkyl groups substituted with C 1 -C 4 alkyl groups are: methylcyclohexyl, dimethylcyclohexyl, etc.
  • phenyl groups substituted with -OH groups and/or with C 1 -C 10 alkyl groups are: methylphenyl, dimethyl- phenyl, trimethylphenyl, t-butylphenyl, 3, 5-di-t-butyl-4- hydroxyphenyl, etc.
  • C 7 -Cg phenylalkyl groups are: benzyl, phen- ylethyl, etc.
  • C 7 -C 9 phenylalkyl groups substituted in the phenyl group with -OH groups and/or alkyl groups having up to 10 carbon atoms are: methylbenzyl, dimethylbenzyl, tri- methylbenzyl, t-butylbenzyl, 3, 5-di-t-butyl-4-hydroxyphenyl, etc.
  • C 3 -C 3 alkenyl groups are: allyl, 2- methallyl, butenyl, pentenyl, hexenyl, etc.
  • the allyl group is preferred.
  • C ⁇ -C 8 acyl groups are, preferably, C ⁇ -C 8 al- kanoyl groups, C 3 -C 8 alkenoyl groups, benzoyl. Examples of these groups are: formyl, acetyl, propionyl, butyryl, penta- noyl, hexanoyl, octanoyl, benzoyl, acryloyl, crotonyl, etc.
  • alkylene groups having up to 18 carbon atoms are: methylene, ethylene, propylene, trimethylene, tet- ramethylene, pentamethylene, 2, 2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene, deca- methylene, etc.
  • the substituent R 5 preferably represents hexamethylene; the substituent R i3 preferably represents ethylene; the substituents R 22 and R 24 preferably represent methylene; the substituent R 2 s preferably represents 2,2- dimethylethylene; the substituent R 26 preferably represents 1, 1-dimethylethylene.
  • An example of a Cs-C 7 cycloalkylene group is cyclohexy- lene.
  • C 1 -C 4 alkylene-di (C 5 -C 7 -cycloalkylene) group is methylenedicyclohexylene.
  • heterocyclic rings with 5-10 atoms when the substituents R 4 , R 5 and Re together with the nitrogen atoms to which they are bound form a heterocyclic ring having 5-10 atoms, are:
  • Heterocyclic rings with 6 atoms are preferred.
  • heterocyclic rings with 5-10 atoms when the substituents R 7 and R 8 together with the nitrogen atoms to which they are bound form a heterocyclic ring having 5-10 atoms, are: 1-pyrrolidyl, piperidine, morpholine, 1-pipe- razinyl, 4-methyl-l-piperazinyl, 1-hexahydroazepinyl, 5,5,7- trimethyl-1-homopiperazinyl, 4,5,5, 7-tetramethyl-l-homopi- perazinyl, etc.
  • the morpholine group is preferred.
  • the substituents R ⁇ 6 and R 20 preferably represent a phenyl group.
  • the substituents X 2 and R 23 preferably represent a direct bond.
  • the substituents Xi, X 3 , R 3 , R 9 , Rn, R 15 and R 2 preferably represent a hydrogen atom.
  • n x is a number between 1 and 25 extremes included, in particular between 2 and 20 or 2 and 10 extremes included;
  • n 2 is a number between 2 and 25 extremes included;
  • n a , n b and n c are a number between 2 and 4 extremes included;
  • n 4 is a number between 2 and 25 extremes included, in particular between 2 and 20 or 2 and 10 extremes included;
  • n 5 and n 5 * are a number between 2 and 25, in particular between 2 and 20 or 2 and 10 extremes included;
  • n 6 is a number between 1 and 25 extremes included, in particular between 1 and 20 or 1 and 10 extremes included;
  • n 7 is a number between 1 and 25 extremes included, in particular between 1 and 20 or 1 and 10 extremes included.
  • Component (a) can be obtained as described, for exam- pie, in patents U.S. 4,684,726, U.S. 4,946,880 and U.S. 5,051,458.
  • Component (c) can be prepared analogously to the known processes, for example, by the reaction of a polyamine having general formula (IVa) with cyanuric chloride in a molar ratio ranging from 1:2 to 1:4, in the presence of anhydrous lithium carbonate, anhydrous sodium carbonate or anhydrous potassium carbonate, in an organic solvent, such as 1,2- dichloroethane, toluene, xylene, benzene, dioxane or t-amyl alcohol, at a temperature ranging from -20°C to +10°C, pref- erably from -10°C to +10°C, in particular from 0°C to +10°C, ⁇ for a time ranging from 2 to 8 hours, followed by the reaction of the product thus obtained with 2, 2, 6, 6-tetramethyl- 4-piperidylamine having general formula (IVb) .
  • an organic solvent such as 1,2- dichloroethane, toluene, xylene, benzene, di
  • the molar ratio between 2, 2, 6, 6-tetramethyl-4-piperidylamine and the polyamine having general formula (IVa) ranges, for example, from 4:1 to 8:1.
  • the quantity of 2, 2, 6, 6-tetramethyl-4- piperidylamine can be added in one portion or more than one portion at intervals of a few hours.
  • the ratio polyamine having general formula (IVa) : cyanuric chloride: 2, 2, 6, 6-tetramethyl-4-piperidylamine having formula (IVb) preferably ranges from 1:3:5 to 1:3:6.
  • component (c) can be prepared as described below.
  • a further 18 g (0.13 moles) of anhydrous potassium carbonate are added and the mixture is heated to 60 °C for a further 6 hours.
  • the solvent is removed by distillation under a light vacuum (200 mbars) and substituted by xylene.
  • 18.2 g (0.085 moles) of N-(2,2,6,6- tetramethyl-4-piperidyl) butylamine and 5.2 g (0.13 moles) of ground sodium hydroxide are added, the mixture is left at reflux temperature for 2 hours and, after a further 12 hours, the water formed during the reaction is removed by azeotropic distillation.
  • the mixture is filtered.
  • the solution is washed with water and dried on Na 2 S0 4 .
  • the solvent is evaporated and the residue is dried at 120°C-130°C under vacuum (0.1 mbar) .
  • the component (c) obtained is a transpar- ent resin.
  • Component (c) can generally be represented by one of the following compounds having general formula (IV-1), (IV- 2) or (IV-3) ; or, component (c) can also be a mixture of the above three compounds :
  • the preferred compound having general formula (IV-1) is:
  • the preferred compound having general formula (IV-2) is: ( IV- 2 ' ) .
  • the preferred compound having general formula (IV-3) is;
  • n 3 is preferably a number ranging from 1 to 20 extremes included.
  • CHIMASSORB 944® CYASORB UV 3346® or DASTAB 1082® as component (b)
  • UVASORB HA 88® as component (c)
  • LO ILITE 62® as component (d)
  • HOSTAVIN N 30® as component (e)
  • UVINUL 5050 H® LICHTSCHUTZSTOFF UV 31® or LUCHEM B 18® as component (f)
  • MARK LA 63® or MARK LA 68® as component (g) .
  • the compounds having general formula (Via) and (VIb) can be used as a mixture or as such, as component (e) for the purposes of the present invention.
  • the ratio (Via) :VIb) ranges, for example, from 20:1 to 1:20, or from 1:10 to
  • terminal groups which saturate the free valences in the compounds having general formula (II) , (IV-1), (IV-2), (IV-3), (V), (Via), (VIb), (VII) and (VIII), depend on the process used for their preparation.
  • the terminal groups can also be modified after the preparation of the compounds .
  • R 7 wherein X represents, for example, a halogen atom, preferably chlorine, and R 7 and R 8 have the same meanings described above, with a compound having general formula (lib) :
  • the terminal group bound to the diamine radical is a hydrogen atom or a compound having general formula (lie) :
  • X represents a halogen atom
  • amine groups which can be used for the purpose are: pyrrolidin-1- yl, morpholine, -NH 2 , -N [ (C ⁇ -C 8 ) -alkyl] 2 and -NR (C ⁇ -C 8 ) alkyl wherein R represents a hydrogen atom or a group having general formula (III) .
  • the terminal group bound to the triazine radical is, for example, a chlorine atom or a group having general formula (IV-a' ) :
  • R ⁇ 0 and Rn have the same meanings described above and the terminal group bound to the amine radical is, for example, a hydrogen atom or a group having general formula (IV-b') :
  • R 10 and Rn have the same meanings described above.
  • R ⁇ 2 represents a hydrogen atom or a methyl group, with a diester of a dicarboxylic acid having general formula Y-OOC-R ⁇ 3 -COO-Y wherein Y represents, for example, methyl, ethyl or propyl and R x3 has the same meanings described above
  • the terminal group bound to the 2, 2, 6, 6-tetramethyl- 4-oxypiperidin-l-yl radical is a hydrogen atom or a group having general formula -CO-R ⁇ 3 -COO-Y
  • the terminal group bound to the diacyl radical is an -O-Y group or a group having general formula (Vb) :
  • the ter- minal group bound to the nitrogen can be, for example, a hydrogen atom and the terminal group bound to the 2- hydroxypropylene radical can be, for example, a group having formula (Via' ) :
  • the terminal group bound to the dimethylene radical can be, for ex- ample, an -OH group and the terminal group bound to the oxygen can be, for example, a hydrogen atom.
  • the terminal groups can also be polyether radicals.
  • the terminal group bound to the 2, 5-dioxopyrrolidine ring is, for example, a hydrogen atom
  • the terminal group bound to the -C(R 20 ) (R 2 ⁇ )- radical is, for example a group having general formula (Vila) or (Vllb) :
  • R i4 , R i5 , R ⁇ 8 and Rig have the same meanings described above .
  • the terminal group bound to the carbonyl radical is, for example, a group having general formula (Villa) :
  • R 27 has the same meanings described above and the terminal group bound to the oxygen is, for example, a group having general formula (Vlllb) :
  • Preferred stabilizing mixtures for the purposes of the present invention are those wherein, in components (a) (g):
  • Ri is a C 1 -C 4 alkyl group, a C 5 -C 8 cycloalkyl group, a phenyl group;
  • R 2 is a C 3 -C ⁇ alkylene group; ni is a number from 1 to 25; - R 3 , Rg, Rn, R 15 and R 2 are each independently a hydrogen atom or a methyl;
  • R 4 , R ⁇ , R ⁇ and R 8 are each independently a hydrogen atom; a C ⁇ -C 8 alkyl group; a C 5 -Cs cycloalkyl group; a phenyl group; a C 7 -C 9 phenylalkyl group; a group having general formula (III); or, the substituents R 7 and R 8 , together with the nitrogen atom to which they are bound, form a heterocyclic ring with 6 atoms;
  • R 5 represents a C 2 -C ⁇ 0 alkylene group; n 2 is a number from 2 to 25 extremes included; - n a , n b and n c , are each independently a number from 2 to 4 extremes included; Rio represents a C ⁇ -C 4 alkyl group;
  • R ⁇ 2 represents a hydrogen atom;
  • R i3 represents an ethylene group;
  • - n 4 is a number from 2 to 25 extremes included;
  • Ri4 and R ⁇ 8 represent a direct bond; a -N (Xi) -CO-X 2 -CO-
  • Ri 6 and R 20 represent a C ⁇ -C 25 alkyl group; a phenyl group;
  • R x and R 2 ⁇ represent a hydrogen atom; a C ⁇ -C 4 alkyl group;
  • Rig represents a C ⁇ -C 25 alkyl group; a group having general formula (III) ; n 6 is a number from 1 to 25 extremes included;
  • R 22 , R 24 , R 25 and R 26 represent a C ⁇ -C 4 alkylene group; - R 23 represents a direct bond; n 7 is a number from 1 to 25 extremes included.
  • Stabilizing mixtures even more preferable for the purposes of the present invention are those wherein component (a) is a compound (a') having formula (I-A 1 ):
  • component (b) is at least one compound having formula (II-B- 1) , (II-B-2) or (II-B-3) :
  • component (c) is at least one compound obtained by reacting a product obtained from the reaction of a polyamine having formula (IVa-1) :
  • component (d) is at least one compound having formula (V-D)
  • component (V-D) wherein n 4 is a number from 2 to 20 extremes included; component (e) is at least one compound wherein n 5 and n 5 * are each independently a number from 2 to 20 extremes included; component (f) is at least one compound having formula (VII- F-l), (VII-F-2) or (VII-F-3) :
  • component (g) is at least one compound having formula (VIII- G) :
  • stabilizing mixture comprising compounds (a) and (b)
  • stabilizing mixture comprising compounds (a) and (c) 3. stabilizing mixture comprising compounds (a) and (d)
  • stabilizing mixture comprising compounds (a) and (f) ;
  • stabilizing mixture comprising compounds (a) and (g) .
  • Particularly preferred are the following stabilizing mixtures : a) stabilizing mixture comprising at least one compound (a') and at least one compound having formula (II-B-1) ; b) stabilizing mixture comprising at least one compound (a 1 ) and at least one compound having formula (II-B-3) ; c) stabilizing mixture comprising at least one compound (a') and a product obtained from the reaction of a polyamine having formula (IVa-1) :
  • the two components are used in a weight ratio ranging from 0.5:1 to 2:1, preferably in a weight ratio 1:1.
  • the above stabilizing mixtures can be used as heat, oxidative degradation and light stabilizers for organic polymers.
  • organic polymers which can be stabilized are: 1.
  • Polymers of mono-olefins and diolefins such as, for ex- ample, polypropylene, polyisobutylene, polybut-1-ene, poly-4- methylpent-1-ene, polyisoprene or polybutadiene; as well as polymers of cyclo-olefins such as, for example, cyclopentene or norbornene; polyethylene (which can be optionally cross- linked) such as, for example, high density polyethylene (HOPE) , high density and high molecular weight polyethylene (HDPE-HMW) , high density and ultrahigh molecular weight polyethylene (HDPE-UHMW) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , branched low density polyethylene (BLDPE) .
  • Polyolefins such as, for example the mono-olefins mentioned in the above paragraph, preferably polyethylene and polypropylene, can be
  • radical polymerization (generally carried out at a high pressure and high temperature) ;
  • a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals generally have one or more ligands such as, for example, oxides, hal- ides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be ⁇ - or ⁇ -coordinated.
  • ligands such as, for example, oxides, hal- ides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be ⁇ - or ⁇ -coordinated.
  • These metal complexes can be in free form or supported on substrates such as, for example, activated magnesium chloride, titanium (III) chloride, alumina or silicon ox- ide.
  • These catalysts can be soluble or insoluble in the reaction medium.
  • the catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal alkyls, oxides of metal alkyls or metal alkyloxanes, these met- als being elements belonging to groups la, Ila and/or Ilia of the Periodic Table.
  • the activators can be conveniently modified with other ester, ether, amine or si- lyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (Du-Pont) , metallocene or "single site catalyst" (SSC) .
  • Copolymers of mono-olefins and diolefins with each other or with other vinyl monomers such as, for example, ethyl- ene/propylene copolymers, linear low density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE) , propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/ hep- tene copolymers, ethylene/octene copolymers, propyle- ne/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacryl- ate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon
  • Hydrocarbon resins for example, C 5 -C 9
  • hydrogenated modifications for example, adhesive agents
  • Polystyrene poly (p-methylstyrene) , poly ( ⁇ -methylstyre- ne) .
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as, for example, styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/ butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethy- lene/propylene/diene terpolymer, block copolymers of styrene such as, for example, styrene/butadiene/styrene, styrene
  • Grafted copolymers of styrene or of -methylstyrene such as, for example, styrene on polybutadiene, styrene on polybutadiene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkylacrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers, styrene and acrylonitrile on
  • Polymers containing halogens such as, for example, poly- chloroprene, chlorinated rubbers, chlorinated or brominated isobutylene-isoprene copolymers ("halobutyl rubber"), chlo- rinated or chlorosulfonated polyethylene, ethylene and chlorinated ethylene copolymers, homopolymers and copolymers of epichlorohydrin, in particular polymers of vinyl compounds containing halogens such as, for example, polyvinyl chloride, polyvinylidenechloride, polyvinyl fluoride or polyvinylidene- fluoride; and also their copolymers such as, for example, vi- nyl chloride/vinylidenechloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate.
  • halobutyl rubber chlorinated or brominated isobutylene-isoprene copolymers
  • Polymers deriving from , ⁇ -unsaturated acids and their derivatives such as, for example, polyacrylates and poly- methacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified with butyl acrylate.
  • Copolymers of monomers according to point (9) with each other or with other unsaturated monomers such as, for example, acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • Homopolymers and copolymers of open-chain ethers or cy-nch ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers .
  • Polyacetals such as, for example, polyoxymethylene and those polyoxymethylenes containing ethylene oxide as comono- mer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides deriving from diamines and dicarboxylic acids and/or aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2, 4, 4-trimethylhexamethylene tereph- thalamide or poly-m-phenylene isophthalamide; and also block copolymers of the above polyamides with polyolefins, olefinic copolymers, ionomers or elastomers chemically bound or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polyte
  • Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1, -dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block co- polyether esters deriving from polyethers with hydroxyl- terminated groups; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
  • Cross-linked polymers deriving from aldehydes on the one hand and from phenols, urea and melamines on the other, such as, for example, phenol/formaldehyde resins, urea/formal- dehyde resins and melamine/formaldehyde resins.
  • Resins based on unsaturated polyesters deriving from co- polyesters of dicarboxyl acids saturated and unsaturated with polyhydric alcohols and vinyl compounds as cross-linking agents, and also the above resins containing halogens and having a good flame-resistance.
  • Cross-linkable acrylic resins deriving from substituted acrylates such as, for example, epoxy acrylates, urethane ac- rylates or polyester acrylates.
  • substituted acrylates such as, for example, epoxy acrylates, urethane ac- rylates or polyester acrylates.
  • Cross-linked epoxy resins deriving from aliphatic, cy- cloaliphatic, heterocyclic or aromatic glycidyl compounds such as, for example, products of diglycidyl ethers of bisphenol A and bisphenol F, which are cross-linked with the usual hardening agents such as, for example, anhydrides or amines, in the presence of or without accelerating agents.
  • Natural polymers such as, for example, cellulose, rubber, gelatine, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resins ("rosins”) and their derivatives.
  • polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylates, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC.
  • polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylates,
  • Natural or synthetic organic materials which are pure monomeric compounds or mixtures of said compounds, such as, for example, mineral oils, animal or vegetable oils, fats or waxes, oils, fats or waxes based on synthetic esters (for example, phthalates, adipates, phosphates, trimellitates) , as well as mixtures of synthetic esters with mineral oils in any weight ratio, in particular those used in spinning compositions, as well as aqueous emulsions of said organic ma- terials.
  • synthetic esters for example, phthalates, adipates, phosphates, trimellitates
  • Aqueous emulsions of natural or synthetic rubbers such as, for example, natural latex or latexes based on carboxy- lated styrene-butadiene copolymers.
  • the present invention also relates to polymeric compo- sitions containing an organic polymer and an effective quantity of the above stabilizing mixtures.
  • the stabilizing mixtures of the present invention are particularly useful in the stabilization of synthetic organic polymers selected from those listed above. They are preferably used in the stabilization of polyolefins, more preferably in the stabilization of polyethylene, polypropylene and their copolymers, of mechanical mixtures consisting of polyethylene and polypropylene, polypropylene with sty- rene/butadiene rubbers (SBR) , or with ethylene/propylene rubbers or with ethylene/propylene/diene rubbers.
  • SBR sty- rene/butadiene rubbers
  • the components of the stabilizing mixtures of the present invention can be added to the polymers to be stabilized individually or mixed with each other.
  • the components can be used, each independently, in a quantity ranging from 0.005% to 3.5%, on the condition that the total quantity of compo- nent (a) and component (b) , (c) , (d) , (e) , (f) or (g) ranges from 0.01% to 5% with respect to the total weight of the polymer to be stabilized.
  • the total quantity of component (a) and component (b) , (c) , (d) , (e) , (f) or (g) ranges from 0.05% to 3%, specifically ranges from 0.05% to 2%, more specifically from 0.1% to 1%, with respect to the total weight of the polymer to be stabilized.
  • the weight ratio between component (a) and component (b) , (c) , (d) , (e) , (f) or (g) preferably ranges from 20:1 to 1:20, in particular from 5:1 to 1:5, more specifically from 2:1 to 1:2.
  • the stabilizing mixtures of the present invention or the single components described above can be incorporated into the organic polymer to be stabilized using known techniques such as, for example, before or during processing; or, these mixtures or components dissolved or dispersed in solvents, can be applied to the polymer to be stabilized, if necessary, after evaporation of the solvents in which they are dissolved or dispersed.
  • the single components of the above mixtures can be added to the organic polymer to be stabilized in the form of powders, granules or masterbatch which contains said components in a concentration ranging from 2.5% to 80%. If necessary, the components of the above stabilizing mixtures can be melted and mixed with each other before incorporation into the organic polymer.
  • the stabilizing mixtures of the present invention or their single components can also be added during the polym- erization process or before cross-linking.
  • the polymeric compositions thus stabilized can be transformed into a wide variety of end-articles such as, for example, films, fibres, tapes, moulding compositions, ligands for paints, adhesives, putties.
  • the present invention therefore also relates to the use of the above polymeric compositions for the production of end-articles.
  • the stabilizing mixtures of the present invention can be combined with other conventional additives or their mix- tures. These additives are added in a quantity ranging from about 0.1% to about 5% by weight with respect to the weight of the polymeric compositions to be stabilized, preferably from about 0.5% to about 3% by weight. Some of the additives used are listed below as an example. 1. Antioxidants
  • Alkylated monophenols such as, for example: 2,6-di-t- butyl-4-methylphenol; 2-t-butyl-4, 6-dimethylphenol; 2,6-di- t-butyl-4-ethylphenol; 2, 6-di-t-butyl-4-n-butylphenol; 2,6- di-t-butyl-4-isobutylphenol; 2 , 6-dicyclopentyl-4-methyl- phenol; 2- ( ⁇ -methylcyclohexyl) -4, 6-dimethylphenol; 2,6-dio- ctadecyl-4-methylphenol; 2, 4, 6-tricyclohexylphenol; 2,6-di- t-butyl-4-methoxymethylphenol; nonylphenols with a linear or branched alkyl chain such as, for example, 2, 6-di-nonyl-4- methylphenol; 2, 4-dimethyl-6- (1 ' -methylundec-1 ' -yl
  • Alkylthiomethylphenols such as, for example: 2, 4-dioc- tylthiomethyl-6-t-butylphenol; 2, 4-dioctylthiomethyl-6-me- thylphenol; 2, 4-dioctylthiomethyl-6-ethylphenol; 2,6-dido- decylthiomethyl-4-nonylphenol .
  • Hydroquinones and alkylated hydroquinones such as, for example: 2, 6-di-t-butyl-4-methoxyphenol; 2, 5-di-t-butyl- hydroquinone; 2, 5-di-t-amylhydroquinone; 2, 6-di-phenyl-4- octadecyloxyphenol; 2, 6-di-t-butylhydroquinone; 2,5-di-t- butyl-4-hydroxyanisol; 3, 5-di-t-butyl-4-hydroxyanisol; 3,5- di-t-butyl-4-hydroxyphenyl stearate; bis (3, 5-di-t-butyl-4- hydroxyphenyl) adipate.
  • 2, 6-di-t-butyl-4-methoxyphenol 2, 5-di-t-butyl- hydroquinone; 2, 5-di-t-amylhydroquinone; 2, 6-di-phenyl-4- octadecyloxyphenol;
  • Tocopherols such as, for example: ⁇ -tocopherol, ⁇ - tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and their mixtures (Vitamin E) .
  • Hydroxylated thiodiphenyl ethers such as, for example 2,2' -thiobis- (6-t-butyl-4-methylphenol) ; 2,2' -thiobis- (4- octylphenol) ; 4,4' -thiobis- ( 6-t-butyl-3-methylphenol) ; 4,4'-thiobis-(6-t-butyl-2-methylphenol) ; 4, 4' -thiobis (3,6- di-s-amylphenol; 4,4* -bis- (2, 6-dimethyl-4-hydroxy-phenyl) disulfide.
  • Alkylidene-bisphenols such as, for example: 2, 2 '-methyl enebis- (6-t-butyl-4-methylphenol) ; 2,2' -methylenebis- (6-t- butyl-4-ethylphenol) ; 2,2' -methylenebis [4-methyl-6- ( ⁇ -meth- ylcyclohexyl) phenol] ; 2, 2 ' -methylenebis (4-methyl-6-cyclo- hexylphenol) ; 2, 2 ' -methylenebis (6-nonyl-4-methyl-phenol) ; 2,2' -methylenebis (4, 6-di-t-butylphenol) ; 2,2' -ethylidene- bis (4, 6-di-t-butylphenol) ; 2, 2 ' -ethylidenebis (6-t-butyl-4- isobutylphenol) ; 2, 2 ' -methylenebis [6- ( ⁇ -methylbenzyl) ;
  • Benzyl compounds containing 0, N or S such as, for example : 3, 5, 3 ' , 5 ' -tetra-t-butyl-4 , 4 ' -dihydroxydibenzyl- ether; octadecyl-4-hydroxy-3, 5-dimethylbenzylmercapto- acetate; tridecyl-4-hydroxy-3, 5-di-t-butyl-benzyl- mercaptoacetate; tris (3, 5-di-t-butyl-4-hydroxybenzyl) amine; bis (4-t-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithiotereph- thalate; bis (3, 5-di-t-butyl-4-hydroxybenzyl) sulfide; iso- octyl-3, 5-di-t-butyl-4-hydroxybenzylmercaptoacetate.
  • Hydroxybenzylated malonates such as, for example: dioctadecyl-2, 2-bis (3, 5-di-t-butyl-2-hydroxybenzyl)malon- ate; dioctadecyl-2- (3-t-butyl-4-hydroxy-5-methylbenzyl) - malonate; didodecylmercaptoethyl-2, 2-bis (3, 5-di-t-butyl-4- hydroxybenzyl)malonate; bis [4- (1, 1, 3, 3-tetramethyl- butyl) phenyl] -2, 2-bis (3, 5-di-t-butyl-4-hydroxybenzyl) - malonate.
  • Aromatic hydroxybenzyl compounds such as, for example: 1, 3, 5-tris (3, 5-di-t-butyl-4-hydroxybenzyl) -2,4, 6-trimethyl- benzene; 1, 4-bis- (3, 5-di-t-butylhydroxybenzyl) -2,3,5, 6-te- tramethylbenzene; 2,4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) phenol.
  • Triazine compounds such as, for example: 2, 4-bis (octyl- mercapto) -6- (3, 5-di-t-butyl-4-hydroxyaniline) -1, 3, 5-tri- azine; 2-octylmercapto-4, 6-bis (3, 5-di-t-butyl-4-hydroxy- aniline) -1, 3, 5-triazine; 2-octylmercapto-4, 6-bis (3, 5-di-t- butyl-4-hydroxyphenoxy) -1, 3, 5-triazine; 2, 4, 6-tris- (3, 5-di- t-butyl-4-hydroxyphenoxy) -1,2, 3-triazine; 1, 3, 5-tris (3, 5-di- t-butyl-4-hydroxybenzyl) isocyanurate; 1, 3 " , 5-tris (4-t-butyl- 3-hydroxy-2, 6-dimethylbenzyl) isocyanurate; 2,4, 6-tris- (3, 5- di-t-butyl
  • Benzylphosphonates such as, for example: dimethyl-2, 5- di-t-butyl-4-hydroxybenzylphosphonate; diethyl-3, 5-di-t- butyl-4-hydroxybenzylphosphonate; dioctadecyl-3, 5-di-t- butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-t-butyl-4- hydroxy-3-methylbenzylphosphonate; calcium salts of monoethyl ester of 3, 5-di-t-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols such as, for example: 4-hydroxylaura- nilide; 4-hydroxystearanilide; octyl-N- (3, 5-di-t-butyl-4- hydroxyphenyl) carbamate.
  • esters of ⁇ - (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propa- nediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxye- thyl) isocyanurate, N,N' -bis (hydroxyethyl) oxamide, 3-thio- undecanol, 3-thiopentadecanol, trimethylhexandiol, trimethy- lolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo- [2.2.2
  • esters of ⁇ - (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, oc- tadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxa- bicyclo [2.2.2] octan
  • esters of ⁇ - (3, 5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, oc- tadecanol, 1, 6-hexandiol, 1, 9-nonandiol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N' -bis (hydroxyethyl) - oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7- trioxabicyclo [2.2.2] octan
  • esters of (3, 5-di-t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexandiol, 1, 9-nonandiol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso- cyanurate, N,N' -bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7-trioxabicyclo [2.2.2] octane
  • vitamin C Ascorbic acid
  • Amine antioxidants such as, for example, N,N'-di- isopropyl-p-phenylenediamine; N,N' -di-s-butyl-p-phenylene- diamine; N,N' -bis (1, 4-dimethylpentyl) -p-phenylenediamine; N,N' -bis (l-ethyl-3-methylpentyl) -p-phenylenediamine; N,N' - bis (1-methylheptyl) -p-phenylenediamine; N,N' -dicyclohexyl- p-phenylenediamine; N,N' -diphenyl-p-phenylenediamine; N,N'- bis (2-naphthyl) -p-phenylenediamine; N-isopropyl-N' -phenyl-p- phenylenediamine; N- (1, 3-dimethylbutyl
  • 2- (2 ' -hydroxyphenyl) benzotriazoles such as, for example: 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole; 2- (3 ' , 5 ' -di-t-butyl-2 ' -hydroxyphenyl) benzotriazole; 2- (5 ' -t-butyl-2 '-hydroxyphenyl) benzotriazole; 2- [2 ' -hydroxy- -5 ' - (1, 1, 3, 3-tetramethylbutyl) phenyl] benzotriazole; 2- (3 ' , - 5 ' -di-t-butyl-2 ' -hydroxyphenyl) -5-chlorobenzotriazole; 2- (3 ' -t-butyl-2 ' -hydroxy-5 ' -methylphenyl) -5-chlorobenzotriazole; 2- (3 ' -sec-butyl-5 ' -t-butyl
  • 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy-; 4-decyloxy-; 4- dodecyloxy-; 4-benzyloxy-; 4, 2 ' , 4 ' -trihydroxy-; 2 ' -hydroxy- 4,4' -dimethoxy.
  • Esters of benzoic acids optionally substituted, such as, for example: phenyl salicylate, 4-t-butylphenyl salicylate, octylphenyl salicylate, benzoyl resorcinol, bis(4-t- butylbenzoyl) resorcinol, dibenzoyl resorcinol, 2,4-di-t- butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3, 5- di-t-butyl-4-hydroxybenzoate, octadecyl-3, 5-di-t-butyl-4- hydroxybenzoate, 2-methyl-4, 6-di-t-butylphenyl-3, 5-di-t-but- yl-4-hydroxybenzoate.
  • benzoyl resorcinol bis(4-t- butylbenzoyl) resorcinol, dibenzoy
  • Acrylates such as, for example, ethyl or isoctyl ⁇ - cyano- ⁇ , ⁇ -diphenylacrylate; methyl ⁇ -carbomethoxycinnamate, methyl or butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate, N- ( ⁇ -carbomethoxy- ⁇ -cy- anovinyl) -2-methylindoline.
  • Nickel compounds such as, for example, complexes of 2,2 ' -thio-bis- [4- (1, 1, 3, 3-tetramethylbutyl) phenol] , for example 1:1 or 1:2 complexes, with or without additional lig- ands such as n-butylamine, triethanolamine or N-cyclohexyl- diethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3, 5-di-t-butyl-benzyl-phos- phonic acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenyl unde- cyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5-hyd- roxypyrazol with or without additional ligands.
  • lig- ands such as n-butylamine, triethanolamine or N-cyclohexyl- diethanolamine, nickel
  • Sterically hindered amines such as, for example: bis- (2,2,6, 6-tetramethyl-4-piperidyl) sebacate; bis (2,2,6, 6-tet- ramethyl-4-piperidyl) succinate; bis (1, 2, 2, 6, 6-pentamethyl- -4-piperidyl) sebacate; bis (l-octyloxy-2, 2, 6, 6-tetramethyl-4- piperidyl) sebacate; bis (1,2,2,6, 6-pentamethyl-4-piperid- yl) n-butyl-3, 5-di-t-butyl-4-hydroxybenzylmalonate; condensation product between N,N' -bis (2, 2, 6, 6-tetramethyl-4-piper- idyl) hexamethylendiamine and 4-t-octylamino-2, 6-di-chloro- 1, 3, 5-triazine; tris (2, 2, 6, 6-tetramethyl-4-piperidinyl) ni- tri-
  • Oxamides such as, for example: 4, 4 ' -dioctyloxyoxanil- ide; 2, 2 ' -diethoxyoxanilide; 2, 2 ' -dioctyloxy-5, 5 ' -di-t-but- oxanilide; 2, 2 ' -didodecyloxy-5, 5 ' -di-t-butoxanilide; 2-eth- oxy-2 ' -ethyloxanilide; N,N' -bis (3-dimethylaminopropyl) oxamide; 2-ethoxy-5-t-butyl-2 ' -ethoxanilide and its mixtures with 2-ethoxy-2 ' -ethyl-5, 4 ' -di-t-butoxanilide; and mixtures of disubstituted ortho- and para-methoxy oxanilides and ix- tures of disubstituted
  • Metal-deactivators such as, for example: N,N' -di-pheny- loxamide, N-salicylal-N' -salicyloyl-hydrazine, N,N'-bis(sa- licyloyl) hydrazine, N,N' -bis (3, 5-di-t-butyl-4-hydroxyphen- ylpropionyl) hydrazine, 3-salicyloylamino-l, 2, 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl di- hydrazide, sebacoyl bisphenylhydrazide, N,N' -diacetyladipo- yl dihydrazide, N,N' -bis (salicyloyl) oxallyl dihydrazide, N,- N' -bis (salicyl
  • Phosphites and phosphonites such as, for example: tri- phenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphi- te, tris (2, 4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-t-butyl-phenyl) pentaerythritol diphosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite,
  • Hydroxylamines such as, for example: N,N-dibenzyl-hydr- oxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxyl- amine; N,N-dilaurylhydroxylamine; N,N-ditetradecylhydrox- ylamine; N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydr- oxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-hepta- decyl-N-octadecylhydroxylamine; N,N-hydroxylamine deriving from hydrogenated tallow amine.
  • Nitrons such as, for example: N-benzyl- ⁇ -phenyl-nitron; N-ethyl- -methyl-nitron; N-octyl- ⁇ -heptyl-nitron; N-lauryl- ⁇ -undecyl-nitron; N-tetradecyl- -tridecyl-nitron; N-hexade- cyl- -pentadecyl-nitron; N-octadecyl- -heptadecyl-nitron; N- hexadecyl- ⁇ -heptadecyl-nitron; N-octadecyl- ⁇ -pentadecyl-ni- tron; N-heptadecyl- ⁇ -heptadecyl-nitron; N-octadecyl- -hexa- decyl-nitron; nitron deriving from hydrogenated tallow
  • Thiosynergists such as, for example: dilauryl thiodipro- pionate; distearyl thiodipropionate.
  • Agents which are capable of destroying peroxides such as, for example, esters of ⁇ -thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimi- dazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide pentaerythritol tet- rakis ( ⁇ -dodecylmercapto) propionate.
  • Stabilizers of polyamide such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
  • Basic co-stabilizers such as, for example: melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, polyurethanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids with a high molecular weight such as, for example, Ca-stearate, Zn-stearate, Mg- stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimo- nium-pyrocatecholate, tin-pyrocatecholate, calcium montan- ate.
  • Basic co-stabilizers such as, for example: melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, derivatives of urea, derivatives of hydrazine, amines, polyamides, polyurethanes, salts
  • Nucleating agents such as, for example: inorganic substances such as talc, metal oxides (for example, titanium dioxide or magnesium oxide) , phosphates, carbonates or sul- fates (preferably of earth-alkaline metals) ; organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzoic acid, adipic acid, diphenyl- acetic acid, sodium succinate, sodium benzoate) ; polymeric compounds such as ionic copolymers ("ionomers”) .
  • inorganic substances such as talc, metal oxides (for example, titanium dioxide or magnesium oxide) , phosphates, carbonates or sul- fates (preferably of earth-alkaline metals) ; organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzoic acid, adipic acid, diphenyl- acetic acid, sodium succinate, sodium benzoate) ;
  • Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres.
  • Other additives such as, for example: plasticizers, lubricants, emulsifying agents, pigments, rheological additives, catalysts, slip agents, optical brighteners, flame- retardants (for example bromurates, chlorurates, phosphor- ates and phosphorous/halogen mixtures) , antistatic agents, blowing agents.
  • Benzofuranones and indolinones such as, for example: 3- [4- (2-acetoxyethoxy) phenyl] -5, 7-di-t-butylbenzofuran-2- one; 5, 7-di-t-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzo- furan-2-one; 3, 3 ' -bis [5, 7-di-t-butyl-3- [4- (2-hydroxyethoxy) phenyl] benzofuran-2-one] ; 5, 7-di-t-butyl-3- (4-ethoxyphenyl) benzofuran-2-one; 3- (4-acetoxy-3, 5-dimethylphenyl) -5,7-di-t- butyl-benzofuran-2-one; 3- (3, 5-dimethyl-4-pivaloyloxyphen- yl) -5,7-di-t-butyl-benzofuran-2
  • Each mixture is charged into a Brabender single-screw extruder with a diameter of 19 mm, a length about 25 times the diameter, equipped with a screw and a 2 mm nozzle.
  • the operating conditions are the following: - screw rate: 60 r.p.m.; temperature of the extruder: 260°C.
  • the product leaves the die in the form of a solid "spa- ghetto" which, after cooling with air at room temperature, is crushed into granules.
  • the granules of polymer obtained as described above are extruded again using a Plasticizer apparatus operating at a temperature of 270 °C and obtaining tapes having a thickness of 40 ⁇ m.
  • the tapes obtained as described above are subjected to accelerated aging using a Xenotest 1200.
  • the operating conditions are the following: temperature of the black panel: 50°C; relative humidity: 50%.
  • Some of the tapes are removed at regular intervals from the aging chamber and are subjected to tensile stress, determining the impact strength which is obviously reduced during the Xenotest exposure period.
  • polypropylene films are produced, having a thickness of 80 ⁇ m containing 1.5% by weight with respect to the weight of the polymer of calcium carbon- ate and 0.4% by weight with respect to the weight of the polymer of the light stabilizers indicated in Table 2.
  • the films thus obtained are subjected to accelerated aging in an Atlas CI 65 Weatherometer (WOM) under the following operating conditions: - temperature of the black panel: 63°C; radiation: 0.40 W/m 2 ; cycle: 102'/18'.
  • WOM Atlas CI 65 Weatherometer
  • the films are removed from the radiation chamber at regular intervals and subjected to tensile stress breaking resistance tests as described in Example 1 and the t 50% is calculated.
  • Samples of natural polypropylene fibres [continuous fibre 18 deniers per filament (dpf) ] containing the following additives : - calcium stearate: 0.05% by weight with respect to the weight of the polymer; bis (2, 4-di-t-butylphenyl) pentaerythritoldiphosphite (ALKANOX P-24 of Great Lakes): 0.1% by weight with respect to the weight of the polymer; - tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate (ANOX IC-14 of Great Lakes): 0.05% by weight with respect to the weight of the polymer; and 0.2% by weight with respect to the weight of the polymer of the light stabilizers indicated in Table 3, undergo ac- celerated aging in an Atlas CI 65 Weatherometer (WOM) under the same operating conditions used in Example 2. The fibres are removed from the aging chamber at regular intervals and subjected to tensile stress breaking resistance tests.
  • T 50% i.e. the exposure time of the fibres to radia- tion in the WOM necessary for obtaining a 50% reduction in the original impact strength, was taken as evaluation criteria of the properties of the additives.
  • Table 3 also shows the results relating to the varia- tion in the yellow index (Yl) , measured with a Macbeth colorimeter, after exposure of the samples for 56 hours to vapours of nitrogen oxide produced by the combustion of n- propane. A lower variation in the yellow index is in correlation with the better properties of the additive used. Also in this case, PRODUCT 1 combined with LOWILITE 62 provided the best results

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des mélanges stabilisants synergiques comprenant deux polyalkylpipéridines spécifiques, dont le poids moléculaire est élevé, et leur utilisation en tant que stabilisants thermiques, agents de stabilité à l'oxydation et photostabilisants de polymères organiques.
PCT/EP1999/007092 1998-09-25 1999-09-22 Melanges stabilisants synergiques WO2000018833A1 (fr)

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ITMI98A002065 1998-09-25
IT1998MI002065A IT1302265B1 (it) 1998-09-25 1998-09-25 Miscele sinergiche stabilizzanti

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092392A2 (fr) * 2000-05-31 2001-12-06 Ciba Specialty Chemicals Holding Inc. Melanges de stabilisants
WO2001092398A2 (fr) * 2000-05-31 2001-12-06 Ciba Specialty Chemicals Holding Inc. Melange de stabilisants
ES2201934A1 (es) * 2000-05-31 2004-03-16 Ciba Specialty Chemicals Holding Inc. Mezclas de estabilizantes.
AU2001262311B2 (en) * 2000-05-31 2006-08-31 Ciba Specialty Chemicals Holding Inc. Stabilizer mixtures
ITMI20110802A1 (it) * 2011-05-10 2012-11-11 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri

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EP0343717A2 (fr) * 1988-05-27 1989-11-29 GREAT LAKES CHEMICAL ITALIA S.r.l. Stabilisants UV pour des polymères organiques
WO1996018667A2 (fr) * 1994-12-12 1996-06-20 Rhone Poulenc Chimie Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
EP0728806A1 (fr) * 1995-02-10 1996-08-28 Ciba-Geigy Ag Mélange de stabilisateurs synergistiques
EP0754723A1 (fr) * 1995-07-21 1997-01-22 Ciba SC Holding AG Mélange de stabilisateurs synergistique
EP0754722A2 (fr) * 1995-07-21 1997-01-22 3V SIGMA S.p.A Compositions pour la stabilisation de polymères synthétiques

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Publication number Priority date Publication date Assignee Title
EP0343717A2 (fr) * 1988-05-27 1989-11-29 GREAT LAKES CHEMICAL ITALIA S.r.l. Stabilisants UV pour des polymères organiques
WO1996018667A2 (fr) * 1994-12-12 1996-06-20 Rhone Poulenc Chimie Nouveaux composes silicones a fonctions amines cycliques steriquement encombrees, utiles pour la stabilisation lumiere et thermique des polymeres
EP0728806A1 (fr) * 1995-02-10 1996-08-28 Ciba-Geigy Ag Mélange de stabilisateurs synergistiques
EP0754723A1 (fr) * 1995-07-21 1997-01-22 Ciba SC Holding AG Mélange de stabilisateurs synergistique
EP0754722A2 (fr) * 1995-07-21 1997-01-22 3V SIGMA S.p.A Compositions pour la stabilisation de polymères synthétiques

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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001092392A2 (fr) * 2000-05-31 2001-12-06 Ciba Specialty Chemicals Holding Inc. Melanges de stabilisants
WO2001092398A2 (fr) * 2000-05-31 2001-12-06 Ciba Specialty Chemicals Holding Inc. Melange de stabilisants
FR2809740A1 (fr) * 2000-05-31 2001-12-07 Ciba Sc Holding Ag Melanges de stabilisants
FR2809738A1 (fr) * 2000-05-31 2001-12-07 Ciba Sc Holding Ag Melanges de stabilisants
WO2001092392A3 (fr) * 2000-05-31 2002-04-25 Ciba Sc Holding Ag Melanges de stabilisants
WO2001092398A3 (fr) * 2000-05-31 2002-05-16 Ciba Sc Holding Ag Melange de stabilisants
NL1018186C2 (nl) * 2000-05-31 2002-08-06 Ciba Sc Holding Ag Stabilisatormengsels.
NL1018188C2 (nl) * 2000-05-31 2002-08-06 Ciba Sc Holding Ag Stabilisatormengsels.
GB2378950A (en) * 2000-05-31 2003-02-26 Ciba Sc Holding Ag Stabilizer mixtures
GB2378952A (en) * 2000-05-31 2003-02-26 Ciba Sc Holding Ag Stabiliser mixtures
BE1014207A3 (fr) * 2000-05-31 2003-06-03 Ciba Sc Holding Ag Melanges de stabilisants.
ES2199696A1 (es) * 2000-05-31 2004-02-16 Ciba Sc Holding Ag Mezclas de estabilizantes
ES2201934A1 (es) * 2000-05-31 2004-03-16 Ciba Specialty Chemicals Holding Inc. Mezclas de estabilizantes.
GB2378952B (en) * 2000-05-31 2004-04-21 Ciba Sc Holding Ag Stabiliser mixtures
GB2378950B (en) * 2000-05-31 2004-04-21 Ciba Sc Holding Ag Stabilizer mixtures
BE1014946A3 (fr) * 2000-05-31 2004-07-06 Ciba Sc Holding Ag Melanges de stabilisants.
AU2001266010B2 (en) * 2000-05-31 2006-06-08 Ciba Specialty Chemicals Holding Inc. Stabilizer mixtures
AU2001276341B2 (en) * 2000-05-31 2006-06-08 Ciba Specialty Chemicals Holding Inc. Stabilizer mixtures
AU2001262311B2 (en) * 2000-05-31 2006-08-31 Ciba Specialty Chemicals Holding Inc. Stabilizer mixtures
KR100786239B1 (ko) 2000-05-31 2007-12-17 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 안정화제 혼합물
US7628936B2 (en) 2000-05-31 2009-12-08 Ciba Specialty Chemicals Corporation Stabilizer mixtures
US7652081B2 (en) 2000-05-31 2010-01-26 Ciba Specialty Chemicals Corporation Stabilizer mixtures
US7820744B2 (en) 2000-05-31 2010-10-26 Ciba Specialty Chemicals Corp. Stabilizer mixtures
ITMI20110802A1 (it) * 2011-05-10 2012-11-11 3V Sigma Spa Miscele di ammine stericamente impedite per la stabilizzazione di polimeri
WO2012153260A1 (fr) * 2011-05-10 2012-11-15 3V Sigma S.P.A. Mélange d'amines à encombrement stérique pour la stabilisation de polymères

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