US20030191239A1 - Stabilizer mixtures - Google Patents

Stabilizer mixtures Download PDF

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US20030191239A1
US20030191239A1 US10/276,091 US27609102A US2003191239A1 US 20030191239 A1 US20030191239 A1 US 20030191239A1 US 27609102 A US27609102 A US 27609102A US 2003191239 A1 US2003191239 A1 US 2003191239A1
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component
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formula
alkyl
compound
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Francois Gugumus
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BASF Performance Products LLC
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Ciba Specialty Chemicals Corp
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Assigned to CIBA SPECIALTY CHEMICALS CORP. reassignment CIBA SPECIALTY CHEMICALS CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GUGUMUS, FRANCOIS
Publication of US20030191239A1 publication Critical patent/US20030191239A1/en
Priority to US11/498,349 priority Critical patent/US7652081B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
    • 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
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
    • C08K5/353—Five-membered rings
    • 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
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • 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
    • 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
    • C08K5/34922—Melamine; Derivatives thereof
    • 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
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond

Definitions

  • the present invention relates to a stabilizer mixture containing one specific low molecular weight alkylated sterically hindered amine compound and one specific high molecular weight alkylated sterically hindered amine compound, the use of this mixture for stabilizing an organic material, in particular a polyolefin, against degradation induced by light, heat or oxidation and the organic material thus stabilized.
  • the present invention relates to a stabilizer mixture containing
  • E 1 is C 1 -C 4 alkyl
  • m 1 is 1, 2or 4,
  • E 2 is C 1 -C 14 alkylene or a group of the formula (a-I)
  • E 3 is C 1 -C 10 alkyl or C 2 -C 10 alkenyl
  • E 4 is C 1 -C 10 alkylene
  • E 5 and E 6 independently of one another are C 1 -C 4 alkyl, cyclohexyl or methylcyclohexyl, and
  • E 2 is C 4 -C 10 alkanetetrayl
  • two of the radicals E 7 are —COO—(C 1 -C 20 alkyl), and
  • E 9 is C 1 -C 24 alkyl
  • E 10 has one of the meanings of E 1 ;
  • E 12 is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkoxy
  • E 13 has one of the meanings of E 1 .
  • E 14 is a group of the formula (a-III)
  • radicals E 15 independently of one another are C 2 -C 12 alkylene, and the radicals E 16 independently of one another are C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl;
  • R 1 , R 3 , R 4 and R 5 independently of one another are hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl,
  • R 2 is C 2 -C 18 alkylene, C 5 -C 7 cycloalkylene or C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), or
  • radicals R 1 , R 2 and R 3 together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or
  • R 4 and R 5 together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring,
  • R 6 is C 1 -C 4 alkyl
  • b 1 is a number from 2 to 50
  • R 7 and R 11 independently of one another are hydrogen or C 1 -C 12 alkyl
  • R 8 , R 9 and R 10 independently of one another are C 2 -C 10 alkylene, and
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 independently of one another are a group of the formula (b-II),
  • R 12 is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted
  • C 7 -C 9 phenylalkyl which is substituted on the phenyl radical by —OH and/or C 1 -C 10 alkyl; or a
  • R 13 has one of the meanings of R 6 ;
  • R 14 , R 15 , R 16 , R 17 and R 18 independently of one another are a direct bond or
  • R 19 has one of the meanings of R 6 .
  • b 2 is a number from 1 to 50;
  • b′ 3 , b′′ 3 and b′′′ 3 independently of one another are a number from 2 to 12,
  • R 20 is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenylalkyl, and
  • R 21 has one of the meanings of R 6 .
  • alkyl having up to 25 carbon atoms examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-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, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,
  • alkoxy having up to 12 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy and dodecyloxy.
  • C 5 -C 12 cycloalkyl examples are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.
  • C 1 -C 4 Alkyl-substituted C 5 -C 12 cycloalkyl is for example methylcyclohexyl or dimethylcyclohexyl.
  • —OH— and/or C 1 -C 10 alkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.
  • CrCgphenylalkyl examples are benzyl and phenylethyl.
  • C7-C 9 Phenylalkyl which is substituted on the phenyl radical by —OH and/or by alkyl having up to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
  • alkenyl having up to 10 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred.
  • the carbon atom in position 1 is preferably saturated.
  • alkylene having up to 18 carbon atoms examples include methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decarnethylene.
  • C 4 -C 10 alkanetetrayl is 1,2,3,4-butanetetrayl.
  • C 5 -C 7 cycloalkylene is cyclohexylene.
  • C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene) is methylenedicyclohexylene.
  • a 6-membered Heterocyclic Ring is Preferred.
  • radicals R 4 and R 5 together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring
  • this ring is for example 1-pyrrolidyl, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or 4,5,5,7tetramethyl-1-homopiperazinyl.
  • Morpholino is particularly preferred.
  • R 15 is preferably a direct bond.
  • b 1 is preferably a number from 2to 25, in particular 2 to 20.
  • b 2 is preferably a number from 1 to 25, in particluar 1 to 20.
  • b′ 3 and b′′′ 3 are preferably 3 and b′′ 3 is preferably 2.
  • the product (B-4) can be prepared analogously to known processes, for example by reacting a polyamine of formula (B-4-1) with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate in an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol at a temperature of from ⁇ 20° C. to +10° C., preferably from ⁇ 10° C. to +10° C., in particular from 0° C.
  • an organic solvent such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol
  • the molar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula (B-4-1) employed is for example from 4:1 to 8:1.
  • the quantity of the 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion or in more than one portion at intervals of a few hours.
  • the molar ratio of polyamine of the formula (B-4-1) to cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the formula (B-4-2) is preferably from 1:3:5 to 1:3:6.
  • a further 18 g (0.13 mol) of anhydrous potassium carbonate are added and the mixture is warmed at 60° C. for a further 6 hours.
  • the solvent is removed by distillation under a slight vacuum (200 mbar) and replaced by xylene.
  • 19.4 g (0.085 mol) of N-(1,2,2,6,6-penta-methyl-4-piperidyl)butylamine and 5.2 g (0.13 mol) of ground sodium hydroxide are added, the mixture is heated at reflux for 2 hours and, for 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 over Na 2 SO 4 .
  • the solvent is evaporated and the residue is dried at 120-130° C. in vacuo (0.1 mbar).
  • the desired product is obtained as a colourless resin.
  • the product (B-4) can, for example, be represented by a compound of the formula (B-4- ⁇ ), (B-4- ⁇ ) or (B-4- ⁇ ). It can also be in the form of a mixture of these three compounds.
  • b 3 is preferably 2 to 20, in particular 2 to 10.
  • the sterically hindered amine compound of component (I) is preferably selected from the group consisting of the following commercial products: TINUVIN 765 (RTM), TINUVIN 144 (RTM), ADK STAB LA-52 (RTM), ADK STAB LA-62 (RTM), SANDUVOR 3056 (RTM), SANDUVOR PR 31 (RTM) and GOODRITE UV 3159 (RTM).
  • N-methylated form (methylation of the nitrogen in the 2,2,6,6-tetramethyl-4-piperidinyl group) of the commercial product DASTIB 845 (RTM) can easily be obtained by known processes for example in analogy to the method described in U.S. Pat. No. 6,046,304, Example 2.
  • the compound so obtained is also preferably used as component (I).
  • the sterically hindered amine compound of component (II) is preferably selected from the group consisting of the following commercial products: CYASORB UV 3529 (RTM), CHIMASSORB 119 (RTM) and ADK STAB LA-63 (RTM).
  • N-methylated form (methylation of the nitrogen in the 2,2,6,6-tetramethyl-4-piperidinyl group) of the commercial products CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM) and UVASORB HA 88 (RTM) can also easily be obtained by known processes for example in analogy to the same method as described above.
  • the compounds so obtained are likewise preferably used as component (II).
  • terminal groups which saturate the free valences in the compounds of the formulae (B-1), (B-3), (B-4- ⁇ ), (B-4- ⁇ ) and (B-4- ⁇ ) depend on the processes used for their preparation.
  • the terminal groups can also be modified after the preparation of the compounds.
  • X is halogen, it is advantageous to replace this, for example, by —OH or an amino group when the reaction is complete.
  • amino groups which may be mentioned are pyrrolidin-1-yl, morpholino, —NH 2 , —N(C 1 -C 8 )alkyl) 2 and —NR(C 1 -C 8 alkyl), in which R is hydrogen or a group of the formula (b-I).
  • R 1 , R 2 , R 3 , R 4 , R 5 and b 1 are as defined above and R 4 * has one of the meanings of R 4 and R 5 * has one of the meanings of R 5 .
  • the terminal group bonded to the carbonyl radical is, for example,
  • the terminal group bonded to the triazine radical is, for example, Cl or a
  • group, and the terminal group bonded to the amino radical is, for example, hydrogen or a
  • a preferred stabilizer mixture is one wherein
  • component (I) is selected from class ( ⁇ -1) and component (II) is selected from class ( ⁇ -1); or
  • component (I) is selected from class ( ⁇ -1) and component (II) is selected from class ( ⁇ -2); or
  • component (I) is selected from class ( ⁇ -1) and component (II) is selected from class ( ⁇ -3); or
  • component (I) is selected from class ( ⁇ -1) and component (II) is selected from class ( ⁇ -4); or
  • component (I) is selected from class ( ⁇ -2) and component (II) is selected from class ( ⁇ -1); or
  • component (I) is selected from class ( ⁇ -2) and component (II) is selected from class ( ⁇ -2); or
  • component (I) is selected from class ( ⁇ -2) and component (II) is selected from class ( ⁇ -3); or
  • component (I) is selected from class ( ⁇ -2) and component (II) is selected from class ( ⁇ -4); or
  • component (I) is selected from class ( ⁇ -3) and component (II) is selected from class ( ⁇ -1); or
  • component (I) is selected from class ( ⁇ -3) and component (II) is selected from class ( ⁇ -2); or
  • component (I) is selected from class ( ⁇ -3) and component (II) is selected from class ( ⁇ -3); or
  • component (I) is selected from class ( ⁇ -3) and component (II) is selected from class ( ⁇ -4); or
  • component (I) is selected from class ( ⁇ -4) and component (II) is selected from class ( ⁇ -1); or
  • component (I) is selected from class ( ⁇ -4) and component (II) is selected from class ( ⁇ -2); or
  • component (I) is selected from class ( ⁇ -4) and component (II) is selected from class ( ⁇ -3); or
  • component (I) is selected from class ( ⁇ -4) and component (II) is selected from class ( ⁇ -4); or
  • component (I) is selected from class ( ⁇ -5) and component (II) is selected from class ( ⁇ -1); or
  • component (I) is selected from class ( ⁇ -5) and component (II) is selected from class ( ⁇ -2); or
  • component (I) is selected from class ( ⁇ -5) and component (II) is selected from class ( ⁇ -3); or
  • component (I) is selected from class ( ⁇ -5) and component (II) is selected from class ( ⁇ -4).
  • m 1 is 1, 2 or 4,
  • E 2 is C 2 -C 10 alkylene or a group of the formula (a-I)
  • E 3 is C 1 -C 4 alkyl
  • E 4 is C 1 -C 6 alkylene
  • E 5 and E 6 independently of one another are C 1 -C 4 alkyl
  • E 2 is C 4 -C 8 alkanetetrayl
  • two of the radicals E 7 are —COO—(C 10 -C 15 alkyl), and
  • two of the radicals E 7 are a group of the formula (a-II);
  • E 9 is C 10 -C 14 alkyl
  • E 12 is C 1 -C 4 alkoxy
  • radicals E 15 independently of one another are C 2 -C 6 alkylene, and
  • radicals E 16 independently of one another are C 1 -C 4 alkyl or C 5 -C 8 cycloalkyl;
  • R 1 and R 3 independently of one another are a group of the formula (b-I),
  • R 2 is C 2 -C 8 alkylene
  • R 4 and R 5 independently of one another are hydrogen, C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or a group of the formula (b-I), or the radicals R 4 and R 5 , together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and
  • b 1 is a number from 2 to 25;
  • R 7 and R 11 independently of one another are hydrogen or C 1 -C 4 alkyl
  • R 8 , R 9 and R 10 independently of one another are C 2 -C 4 alkylene, and
  • X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 and X 8 independently of one another are a group of the formula (b-II),
  • R 12 is hydrogen, C 1 -C 4 alkyl, C 5 -C 8 cycloalkyl or a group of the formula (b-I);
  • R 14 , R 15 , R 16 , R 17 and R 11 independently of one another are a direct bond or C 1 -C 4 alkylene, and
  • b 2 is a number from 1 to 25;
  • b′ 3 , b′′ 3 and b′′′ 3 independently of one another are a number from 2 to 4, and
  • R 20 is hydrogen, C 1 -C 4 alkyl, C 5 -C 8 cycloalkyl, phenyl or benzyl.
  • a further preferred embodiment corresponds to
  • component (I) is a compound of the formula (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-4-a) or (A-5-a); and
  • component (II) is a compound of the formula (B-1-a), (B-1-b), (B-1-c), (B-2-a), (B -3-a) or a product (B-4-a);
  • b 1 is a number from 2 to 20;
  • b 2 is a number fromn 1 to 20;
  • a product (B-4a) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (B-4-1-a) with cyanuric chloride, with a compound of the formula (B-4-2-a).
  • Component (I) is preferably the compound of the formula (A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-4-a) or (A-5-a); and component (II) is preferably the compound of the formula (B-1-c) or (B-2-a).
  • Component (I) is in particular the compound of the formula (A-1-b) and component (II) is in particular the compound of the formula (B-1-c) or (B-2-a).
  • Preferred examples of stabilizer mixtures according to the present invention are:
  • TINUVIN 765 corresponds to the compound of the formula (A-1-b).
  • TINUVIN 144 corresponds to the compound of the formula (A-1-c).
  • a further preferred embodiment of this invention relates to a stabilizer mixture containing additionally
  • the pigment (component (X-1)) may be an inorganic or organic pigment.
  • inorganic pigments examples include titanium dioxide, zinc oxide, carbon black, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide, lead oxide and so on.
  • organic pigments examples include azo pigments, anthraquinones, phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines, perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.
  • a particularly preferred pigment is titanium dioxide, optionally in combination with an organic pigment.
  • UV absorber examples include a 2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an ester of substituted or unsubstituted benzoic acid, an acrylate, an oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinol or a formamidine.
  • the 2-(2′-hydroxyphenyl)benzotriazole is e.g. 2-(2′-hydroxy-5′-methylphenyl)-benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-4′-octyl
  • the 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy or 2′-hydroxy-4,4′-dimethoxy derivatives.
  • the ester of a substituted or unsubstituted benzoic acid is for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • the acrylate is for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate or N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • the oxamide is 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 or its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide or mixtures of ortho- and para-methoxy-disubstituted oxanilides or mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • the 2-(2-hydroxyphenyl)-1,3,5-triazine is for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine
  • the monobenzoate of resorcinol is for example the compound of the formula
  • the formamidine is for example the compound of the formula
  • the UV absorber is in particular a 2-(2′-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone or a hydroxyphenyltriazine.
  • the stabilizer mixture according to this invention is suitable for stabilizing organic materials against degradation induced by light, heat or oxidation.
  • organic materials are the following:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high 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), (VLDPE) and (ULOPE), or polyvinyl cyclohexane.
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid coplymers and their salts (
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Copolyrners of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrenelisoprene/styrene, st
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlor
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytet
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acrylates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplasfic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplasfic PUR, PC/thermoplastic PUR, POM/acrylate, P
  • Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • Aqueous emulsions of natural or synthetic rubber e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.
  • This invention therefore additionally relates to a composition comprising an organic material subject to degradation induced by light, heat or oxidation and the stabilizer mixture described above.
  • a further embodiment of the present invention is a method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material the stabilizer mixture described above.
  • the organic material is preferably a synthetic polymer, in particular from one of the above groups.
  • Polyolefins are preferred and polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer are particularly preferred.
  • Polypropylene containing talc and/or other fillers e.g. CaCO 3
  • Pigmented polyolefins and pigmented polyamides are further preferred.
  • Acrylonitrile/butadiene/styrene is also preferred as organic material.
  • the components (I), (II) and optionally (X-1) and/or (X-2) may be added to the organic material to be stabilized either individually or mixed with one another.
  • the total amount of the two sterically hindered amine compounds (components (I) and (II)) in the organic material to be stabilized is preferably 0.005 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the organic material.
  • the pigment (component (X-1)) is optionally present in the organic material in an amount of preferably 0.01 to 10%, in particular 0.05 to 1%, relative to the weight of the organic material.
  • the UV absorber (component (X-2) is optionally present in the organic material in an amount of preferably 0.01 to 1%, in particular 0.05 to 0.5%, relative to the weight of the organic material.
  • the total amount of component (X-3) (the pigment in combination with the UV absorber) is preferably 0.01 to 10%, relative to the weight of the organic material.
  • the weight ratio of the UV absorber to the pigment is for example 2:1 to 1:10.
  • titanium dioxide is preferably present in the organic material in an amount of 0.01 to 5%, relative to the weight of the organic material, and the organic pigment may be present in an amount of, for example, 0.01 to 2%, relative to the weight of the organic material.
  • the weight ratio of components (I):(II) is for example 1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
  • the weight ratio of the components (I) and (II):(X-1) is for example 1:100 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
  • the weight ratio of the components (I) and (II):(X-2) is for example 1:5 to 20:1, preferably 1:2to2:1.
  • the weight ratio of the components (I) and (II):(X-3) is for example 1:100 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
  • the above components can be incorporated into the organic material to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic material, if necessary with subsequent evaporation of the solvent.
  • the components can be added to the organic material in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.
  • the components (I) and (II) and optionally (X-1) and/or (X-2) can be melt blended with each other before incorporation in the organic material. They can be added to a polymer before or during the polymerization or before the crosslinking.
  • the materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or pufties.
  • the stabilized material may additionally also contain various conventional additives, for example:
  • Alkylated monoDhenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butyl-phenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methyl-phenol, 2,4-dimethyl-6-(1′-methylundec
  • Alkylthiomethvlphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
  • Hydroquinones and alkvlated hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyloctadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy-phenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyloctade
  • 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-amylpheriol), 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-amylpheriol), 4,4′-
  • 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-cyclohexyl-phenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)
  • O-, N- and S-benzyl compounds for example 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiotereph-thalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hydroxvbenzvlated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hydroxvphenvl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7
  • esters of ⁇ -(5-tert-butvl-4-hydroxy-3-methylphenyl)progionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabi
  • esters of ⁇ -(3,5-dicvclohexyl-4-hydroxvlhenvl)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)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oc
  • esters of 3,5-di-tert-butyl-4-hvdroxyDhenyl 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)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane
  • Aminic antioxidants for example N,N′-di-isopropyl-p-phenylenediamine, N,N′-di-sec-butyl-p-phenylenediamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N′-bis(1-methylheptyl)-p-phenylenediamine, N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine, N,N′-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-N-phenyl
  • Nickel compounds for example nickel complexes of 2,2′-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexy(diethanolamine, 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-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexy(diethanolamine, nickel dibutyldithiocarba
  • 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-hydroxy-phenylpropionyl) hydrazine , 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)-oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl-hydrazide, N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyl dihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosIhonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol
  • Hydroxylamiries 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-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitron
  • 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-mercaptobenzimidazole, 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-mercaptobenzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ -dodecylmercap
  • Basic co-stabilisers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
  • Basic co-stabilisers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium
  • Nucleating agents for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (“ionomers”).
  • inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (“ionomers
  • Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the weight ratio of the total amount of components (I) and (II) and optionally (X-1) and/or (X-2) to the total amount of the conventional additives can be, for example, 100:1 to 1:100.
  • the material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 min at 260° C. to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm ⁇ 25 mm are cut out of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying).
  • the synergistic effect of two coadditivs (( ⁇ ) and ( ⁇ )) is determined by a comparison of the calculated T 0.1 value with the actually measured T 0.1 value.
  • the T 0.1 values are calculated on the basis of the additivity law (B. Ranby and J. F.

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EP00810902 2000-10-02
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WO2005033202A1 (ja) * 2003-10-02 2005-04-14 Polyplastics Co., Ltd. ポリアセタール樹脂組成物
WO2005054353A1 (en) * 2003-11-21 2005-06-16 Ciba Specialty Chemicals Holding Inc. Weatherfast pigmented polystyrene
US20060124904A1 (en) * 2002-04-12 2006-06-15 Francois Gugumus Stabilizer mixtures
US20080139702A1 (en) * 2004-08-06 2008-06-12 Phb Industrial S.A. Use of Fatty Alcohols as Plasticizer to Improve the Physical-Mechanical Properties and Processability of Phb and its Co-Polymers
EP2154190A1 (de) * 2008-08-01 2010-02-17 Borealis AG Polypropylenzusammensetzung mit geringem Anteil an flüchtigen Elementen
US9095189B2 (en) * 2005-09-16 2015-08-04 Arkema France Aging-resistant copolymers comprising polyamide blocks and polyether blocks
TWI504659B (zh) * 2005-06-07 2015-10-21 Ciba Sc Holding Ag 抗刮的聚烯烴

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US6828364B2 (en) 2000-07-14 2004-12-07 Ciba Specialty Chemicals Corporation Stabilizer mixtures
ITMI20012085A1 (it) 2000-10-17 2003-04-09 Ciba Sc Holding Ag Polpropilene metallocene stabilizzato
TWI273115B (en) 2000-12-12 2007-02-11 Ciba Sc Holding Ag Improved weatherability of flame retardant polyolefin
JP4996070B2 (ja) * 2004-07-09 2012-08-08 三井化学株式会社 樹脂組成物およびその用途
JP6046482B2 (ja) * 2012-12-21 2016-12-14 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
WO2015038467A1 (en) 2013-09-13 2015-03-19 Dow Global Technologies Llc Peroxide-crosslinkable compositions and processes for their manufacture
JP6497696B2 (ja) * 2014-12-02 2019-04-10 株式会社Ｎｕｃ 架橋性樹脂組成物および電線・ケーブル
SA116370295B1 (ar) * 2015-02-20 2016-12-06 باسف اس اى رقائق، وأشرطة وفتائل أحادية من البولي أوليفين مثبتة للضوء

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US4198334A (en) * 1975-11-07 1980-04-15 Ciba-Geigy Corporation Substituted malonic acid derivatives and their use as stabilizers
US4086204A (en) * 1975-12-04 1978-04-25 Chimosa Chimica Organica S.P.A. Novel polytriazine compounds
US4108829A (en) * 1975-12-18 1978-08-22 Chimosa Chimica Organica S.P.A. Piperidyl-triazine derivatives as stabilizers for synthetic polymers
US4331586A (en) * 1981-07-20 1982-05-25 American Cyanamid Company Novel light stabilizers for polymers
US4692486A (en) * 1981-10-16 1987-09-08 Ciba-Geigy Corporation Synergistic mixture of low-molecular and high-molecular polyalkylpiperidines
US4477615A (en) * 1982-05-19 1984-10-16 Apital Produzioni Industriali S.P.A. Polypiperidinyl stabilizing agents for polymer materials
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US4619956A (en) * 1985-05-03 1986-10-28 American Cyanamid Co. Stabilization of high solids coatings with synergistic combinations
US4863981A (en) * 1986-06-30 1989-09-05 Ciba-Geigy Corporation Synergistic mixture of stabilizers
US4929652A (en) * 1987-05-05 1990-05-29 Ciba-Geigy Corporation Polyolefins stabilized against damage caused by light
US5071981A (en) * 1990-03-19 1991-12-10 The B. F. Goodrich Company Alkylated oxo-piperanzinyl-triazine
US5679733A (en) * 1992-06-02 1997-10-21 Clariant Finance (Bvi) Limited Solid Solution of low molecular weight and high molecular weight hals
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060124904A1 (en) * 2002-04-12 2006-06-15 Francois Gugumus Stabilizer mixtures
US7595008B2 (en) 2002-04-12 2009-09-29 Ciba Specialty Chemicals Corporation Stabilizer mixtures
WO2005033202A1 (ja) * 2003-10-02 2005-04-14 Polyplastics Co., Ltd. ポリアセタール樹脂組成物
WO2005054353A1 (en) * 2003-11-21 2005-06-16 Ciba Specialty Chemicals Holding Inc. Weatherfast pigmented polystyrene
US20050148705A1 (en) * 2003-11-21 2005-07-07 Adams John W. Weatherfast pigmented polystyrene
US20080139702A1 (en) * 2004-08-06 2008-06-12 Phb Industrial S.A. Use of Fatty Alcohols as Plasticizer to Improve the Physical-Mechanical Properties and Processability of Phb and its Co-Polymers
TWI504659B (zh) * 2005-06-07 2015-10-21 Ciba Sc Holding Ag 抗刮的聚烯烴
US9095189B2 (en) * 2005-09-16 2015-08-04 Arkema France Aging-resistant copolymers comprising polyamide blocks and polyether blocks
EP2154190A1 (de) * 2008-08-01 2010-02-17 Borealis AG Polypropylenzusammensetzung mit geringem Anteil an flüchtigen Elementen

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ITMI20011133A0 (it) 2001-05-29
GB2378951A (en) 2003-02-26
FR2809739A1 (fr) 2001-12-07
MX283566B (es) 2011-02-01
KR20030007694A (ko) 2003-01-23
CA2408651A1 (en) 2001-12-06
ITMI20011133A1 (it) 2002-11-29
MXPA02011759A (es) 2003-04-25
CN1432042A (zh) 2003-07-23
JP2003535206A (ja) 2003-11-25
FR2809739B1 (fr) 2004-06-25
AU2001262311B2 (en) 2006-08-31
AU6231101A (en) 2001-12-11
US7652081B2 (en) 2010-01-26
BR0111240B1 (pt) 2011-12-13
WO2001092393A2 (en) 2001-12-06
NL1018187A1 (nl) 2001-12-03
WO2001092393A3 (en) 2002-04-04
IT1324892B (it) 2004-12-02
GB2378951A8 (en) 2003-03-18
GB2378951B (en) 2003-12-31
US20060270763A1 (en) 2006-11-30
CA2408651C (en) 2012-10-16
ES2208129B1 (es) 2005-08-01
ES2208129A1 (es) 2004-06-01
KR100786241B1 (ko) 2007-12-17
BR0111240A (pt) 2003-06-10
BE1014206A3 (fr) 2003-06-03
JP5111712B2 (ja) 2013-01-09
NL1018187C2 (nl) 2001-12-28
CN1222565C (zh) 2005-10-12
GB0228156D0 (en) 2003-01-08
DE10196267T1 (de) 2003-05-15

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