Classifications

• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/005—Stabilisers against oxidation, heat, light, ozone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—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
  • C08K5/16—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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/267—Magnesium carbonate

Definitions

• the present invention relates to a stabilizer mixture containing a sterically hindered amine compound, a Ca compound and an Zn or Mg compound, the use of this mixture for stabilizing a polyolefin against degradation induced by light, heat or oxidation and the polyolefin thus stabilized.
• the present invention relates to a stabilizer mixture containing
• component (C) is Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when component (B) is calcium stearate.
• Component (C) is in particular Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when component (B) is an organic salt of Ca.
• the sterically hindered amine is preferably a compound containing at least one group of the formula (I) or (II)
• G is hydrogen or methyl
• G 1 and G 2 independently of one another, are hydrogen, methyl or together are a substituent ⁇ O.
• n 1 is a number from 1 to 4
• G and G 1 independently of one another, are hydrogen or methyl
• G 11 is hydrogen, O ⁇ , hydroxyl, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 7 -C 12 aralkyl, C 1 -C 18 alkoxy, C 5 -C 8 cycloalkoxy, C 7 -C 9 phenylalkoxy, C 1 -C 8 alkanoyl, C 3 -C 5 alkenoyl, C 1 -C 18 alkanoyloxy, glycidyl or a group of the formula —CH 2 CH(OH)-Z, in which Z is hydrogen, methyl or phenyl, G 11 preferably being H, C 1 -C 4 alkyl, allyl, benzyl, acetyl or acryloyl, and G 12 , if n 1 is 1, is hydrogen, C 1 -C 18 alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoe
• G 12 if n 1 is 2, is C 2 -C 12 alkylene, C 4 -C 12 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxylic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, where each dicarboxylic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ 12 groups, G 12 , if n 1 is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxy
• carboxylic acid radicals mentioned above are in each case taken to mean radicals of the formula (—CO) x R, where x is as defined above, and the meaning of R arises from the definition given.
• Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• C 3 -C 8 alkenyl G 11 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.
• C 3 -C 8 alkynyl G 11 is preferably propargyl.
• C 7 -C 12 aralkyl G 11 is, in particular, phenethyl, especially benzyl.
• C 1 -C 18 alkoxy G 11 is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy.
• C 5 -C 8 cycloalkoxy G 11 is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy.
• C 7 -C 9 phenylalkoxy is, for example, benzyloxy.
• C 1 -C 8 alkanoyl G 11 is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and C 3 -C 5 alkenoyl G 11 is in particular acryloyl.
• C 1 -C 18 alkanoyloxy G 11 is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.
• G 12 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
• G 12 is a monovalent silyl radical, it is, for example, a radical of the formula -(C j H 2j )—Si(Z′) 2 Z′′, in which j is an integer in the range from 2 to 5, and Z′ and Z′′, independently of one another, are C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
• G 12 is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl or bicycloheptenedicarbonyl radical or a group of the formula
• G 12 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.
• G 12 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
• G 12 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
• G and G 1 are hydrogen, G 11 is hydrogen or methyl, n 1 is 2 and G 12 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 carbon atoms.
• polyalkylpiperidine compounds from this class are the following compounds:
• n 2 is the number 1, 2 or 3
• G, G 1 and G 11 are as defined under (a′)
• G 13 is hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 1 -C 18 alkanoyl, C 3 -C 5 alkenoyl, benzoyl or a group of the formula
• G 14 if n 2 is 1, is hydrogen, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl, C 1 -C 4 alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula —CH 2 —CH(OH)-Z or of the formula —CONH-Z, in which Z is hydrogen, methyl or phenyl;
• G 14 if n 2 is 2, is C 2 -C 12 alkylene, C 6 -C 12 arylene, xylylene, a —CH 2 —CH(OH)—CH 2 group or a —CH 2 —CH(OH)—CH 2 —O-D—O— group, in which D is C 2 -C 10 alkylene, C 6 -C 15 arylene, C 6 -C 12 cycloalkylene, or, provided that G 13 is not alkanoyl, alkenoyl or benzoyl, G 14 can alternatively be 1-oxo-C 2 -C 12 alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or alternatively the group —CO—, G 14 , if n 2 is 3, is a group
• G 13 and G 14 together can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
• Any C 5 -C 7 cycloalkyl substituents are, in particular, cyclohexyl.
• C 7 -C 8 aralkyl G 13 is, in particular, phenylethyl or especially benzyl.
• C 2 -C 5 hydroxyalkyl G 13 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.
• C 1 -C 18 alkanoyl G 13 is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and C 3 -C 5 alkenoyl G 13 is, in particular, acryloyl.
• C 2 -C 8 alkenyl G 14 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
• G 14 as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamide-substituted C 1 -C 4 alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.
• Any C 2 -C 12 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
• Any C 6 -C 15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4′-diphenylene.
• C 6 -C 12 cycloalkylene is, in particular, cyclohexylene.
• G 14 as 1 -oxo-C 2 -C 12 alkylene is preferably a group
• polyalkylpiperidine compounds from this class are the following compounds:
• n 3 is the number 1 or 2
• G, G 1 and G 11 are as defined under (a′)
• G 15 if n 3 is 1, is C 2 -C 8 alkylene, C 2 -C 8 hydroxyalkylene or C 4 -C 22 acyloxyalkylene, and if n 3 is 2, G 15 is the (—CH 2 ) 2 C(CH 2 —) 2 group.
• C 2 -C 8 alkylene or C 2 -C 8 hydroxyalkylene G 15 is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
• C 4 -C 22 acyloxyalkylene G 15 is, for example, 2-ethyl-2-acetoxymethylpropylene.
• polyalkylpiperidine compounds from this class are the following compounds:
• a compound of the formula (Id-3) is preferred.
• Any C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
• Any C 1 -C 18 alkyl substituents can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
• Any C 2 -C 6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
• C 3 -C 5 alkenyl G 17 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
• C 7 -C 9 aralkyl G 17 , T 1 and T 2 are, in particular, phenethyl or especially benzyl. If T 1 and T 2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
• C 2 -C 4 hydroxyalkyl G 17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
• C 6 -C 10 aryl G 17 , T 1 and T 2 are, in particular, phenyl or a- or ,-naphthyl, which are unsubstituted or substituted by halogen or C 1 -C 4 alkyl.
• C 2 -C 12 alkylene G 17 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
• C 4 -C 12 alkenylene G 17 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.
• C 6 -C 12 arylene G 17 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4′-diphenylene.
• C 2 -C 12 alkanoyl D′′ is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.
• C 2 -C 10 alkylene, C 6 -C 15 arylene or C6-C 12 cycloalkylene D′ have, for example, one of the definitions given for D under (b′).
• polyalkylpiperidine compounds from this class are the following compounds:
• n 5 is the number 1 or 2
• G 18 is a group of the formula
• G and G 11 are as defined under (a′), and G 1 and G 2 are hydrogen, methyl or, together, are a substituent ⁇ O,
• E is —O— or -ND′′′-
• A is C 2 -C 6 alkylene or —(CH 2 ) 3 —O— and
• x 1 is the number 0 or 1
• D′′′ is hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl or C 5 -C 7 cycloalkyl,
• G 19 is identical to G 18 or is one of the groups —N(G 21 )(G 22 ), -OG 23 , —N(H)(CH 2 OG 23 ) or —N(CH 2 OG 23 ) 2 ,
• G 21 is C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 4 -hydroxyalkyl or a group of the formula
• G 22 is C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl
• G 23 is hydrogen, C 1 -C 12 alkyl or phenyl, or G 21 , and G 22 together are C 4 -C 5 alkylene or C 4 -C 5 oxaalkylene, for example —CH 2 CH 2 —O—CH 2 CH 2 —, or a group of the formula —CH 2 CH 2 —N(G 11 )—CH 2 CH 2 —.
• Any C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
• Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4- hydroxybutyl.
• Any C 5 -C 7 cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
• C 2 -C 6 alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
• G 21 and G 22 together are C 4 -C 5 alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
• polyalkylpiperidine compounds from this class are the compounds of the following formulae:
• R′ has the same meaning as in compound 76.
• a preferred example from this class is the following compound:
• Examples of 2,2,6,6-polyalkylpiperidine compounds from this class are the compounds of the following formulae, where m 1 to m 14 is a number from 2 to about 200, preferably 2 to 100, for example 2 to 50, 2 to 40 or 3 to 40 or 4 to 10.
• the end group bonded to the —O— can be, for example, hydrogen or a group —CO—(CH 2 ) 2 —COO—Y or —CO—(CH 2 ) 4 —COO—Y, respectively, with Y being hydrogen or C 1 -C 4 alkyl and the end group bonded to the diacyl can be, for example, —O—Y or a group
• the end group bonded to the amino residue can be, for example, a group
• [0200] and the end group bonded to the diacyl residue can be, for example, Cl.
• the end group bonded to the triazine residue can be, for example, chlorine or a group
• the end group bonded to the diamino group can be, for example, hydrogen or a group
• Suitable amino groups are typically: pyrrolidin-1-yl, morpholino, —NH 2 , —N(C 1 -C 8 alkyl) 2 and —NY′(C 1 -C 8 alkyl) wherein Y′′ is hydrogen or a group of the formula
• the end group bonded to the 2,2,6,6-tetramethylpiperidin-4-ylamino residue can be, for example, hydrogen and the end group bonded to the 2-hydroxypropylene residue can be, for example,
• the end group bonded to the —O— can be, for example, hydrogen or
• the end group bonded to the diacyl residue can be, for example, —OCH 3 or Cl.
• the end group bonded to the —O— can be, for example, hydrogen or
• the end group bonded to the diacyl radical can be, for example, —OCH 3 or Cl.
• the end group bonded to the —O— can be, for example, hydrogen or
• the end group bonded to the diacyl radical can be, for example, —OCH 3 or Cl.
• the end group bonded to the —CH 2 — can be, for example, hydrogen and the end group bonded to the ester residue can be, for example,
• the end group bonded to the —CH 2 — can be, for example, hydrogen and the end group bonded to the ester residue can be, for example,
• the end group bonded to the —CH 2 — can be, for example, hydrogen and the end group bonded to the amide residue can be, for example,
• the end group bonded to the triazine residue can be, for example, chlorine or a group
• the end group bonded to the diamino residue can be, for example, hydrogen or a group
• Suitable amino groups are typically: pyrrolidin-1-yl, morpholino, —NH 2 , —N(C 1 -C 8 alkyl) 2 and —NY′(C 1 -C 8 alkyl) wherein Y′ is hydrogen or a group of the formula
• the end group bonded to the diamino residue can be, for example, hydrogen and the end group bonded to the —CH 2 CH 2 — residue can be, for example,
• the end group bonded to the diamino residue can be, for example, hydrogen and the end group bonded to the diacyl residue can be, for example, Cl.
• R′′′ is a group of the formula (95-I), and m′ 15 and m′′ 15 are each a number from 0 to 200, preferably 0 to 100, in particular 0 to 50, with the proviso that m′ 15 +m′′ 15 is a number from 2 to 200, preferably 2 to 100, in particular 2 to 50.
• the end group bonded to the diamino residue can be, for example, hydrogen and the end group bonded to the —CH 2 CH 2 — group can be, for example, halogen, in particular Cl or Br.
• polymeric compounds are:
• n 16 and m 16 * are a number from 2 to 50.
• the compounds of the formulae (96-I) and (96-II) can be obtained together as a mixture and therefore, can also be employed as such.
• the (96-I):(96-II) weight ratio is, for example, from 20:1 to 1:20 or from 1:10 to 10:1.
• the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a
• the terminal group bonded to the dimethylene radical can be, for example, —OH
• the terminal group bonded to the oxygen can be, for example, hydrogen.
• the terminal groups can also be polyether radicals.
• G 24 , G 25 , G 26 , G 27 and G 28 independently of one another, are a direct bond or C 1 -C 10 alkylene, G 11 is as defined under (a′) and m 17 is a number from 1 to 50.
• the end group bonded to the >C ⁇ O group can be, for example,
• m 18 is a number in the range from 2 to 200, preferably 2 to 100, in particular 2 to 50.
• the end group bonded to the —CH 2 — residue can be, for example, hydrogen and the end group bonded to the —CH(CO 2 R IV )— residue can be, for example, —CH ⁇ CH—COOR IV .
• G 11 is as defined under (a′)
• G 29 and G 32 independently of one another, are a direct bond or a —N(X 1 )—CO-X 2 —CO—N(X 3 )— group, where X 1 and X 3 , independently of one another, are hydrogen, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula (99-I)
• X 2 is a direct bond or C 1 -C 4 alkylene
• G 30 , G 31 , G 34 and G 35 independently of one another, are hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or phenyl
• G 33 is hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl, phenyl or a group of the formula (99-1)
• m 19 is a number from 1 to 50.
• the end group bonded to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen
• the end group bonded to the —C(G 34 )(G 35 )— radical can be, for example,
• G 11 is hydrogen or methyl
• m 19 is a number from 1 to 25.
• m′ 20 , m′′ 20 and m′′′ 20 are a number from 2 to 12
• G 36 is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenylalkyl
• G 11 is as defined under (a′).
• a preferred product has the Chemical Abstracts-CAS No. 136 504-96-6 (Compound 100-A).
• the above reaction product can be represented for example by a compound of the formula 100-1, 100-2 or 100-3. It can also be in the form of a mixture of these three compounds.
• m 20 is preferably 1 to 20.
• G 11 is as defined under (a′)
• G 37 is C 1 -C 10 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl or C 1 -C 10 alkyl-substituted phenyl
• G 38 is C 3 -C 10 alkylene and m 21 is a number from 1 to 50.
• the terminal group bonded to the silicon atom can be, for example, (G 37 ) 3 Si—O—, and the terminal group bonded to the oxygen can be, for example, —Si(G 37 ) 3 .
• the compounds of the formula (101) can also be in the form of cyclic compounds if m 21 is a number from 3 to 10, i.e. the free valences shown in the structural formula then form a direct bond.
• m 12 being a number from 1 to 20.
• alkyl examples are 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-ethyl-hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
• n 6 is the number 1 or 2
• G and G 11 are as defined under (a′)
• G 14 is as defined under (b′)
• G 14 cannot be —CONH-Z and —CH 2 —CH(OH)—CH 2 —O-D—O—.
• radicals G 39 independently of one another, are a group of the formula (Ii-1)
• G 40 is C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl
• G 41 is C 2 -C 12 alkylene
• G 42 is hydrogen, C 1 -C 8 alkyl, —O ⁇ , —CH 2 CN, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl, C 7 -C 9 phenylalkyl which is substituted on the phenyl radical by C 1 -C 4 alkyl; or C 1 -C 8 acyl.
• Alkyl is for example C 1 -C 4 alkyl, in particular methyl, ethyl, propyl or butyl.
• Cycloalkyl is preferably cyclohexyl.
• Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.
• Alkenyl is preferably allyl.
• Phenylalkyl is preferably benzyl.
• Acyl is preferably acetyl.
• the sterically hindered amine compound (component (A)) is preferably one of the above compounds 1 to 106.
• the compounds 5, 10, 13, 14, 24, 25, 36-a, 36-b, 36-d, 49-a-I, 49-e, 63, 75, 76, 80-a, 81, 84-1, 84-2, 92, 93, 96-I, 96-II, 97-I, 97-II, 99-I, 100-A, 101-I, 105 and 106 are of interest.
• the compounds 13, 14, 36-a, 36-b, 36-d, 76, 81, 84-I, 96-I, 96-II, 100-A, 101-I, 105 and 106 are preferred.
• the compounds 13, 14, 36-d, 81, 84-1, 96-I, 96-II, 100-A, 101-I, 105 and 106 are particularly preferred.
• Examples of an organic salt of Ca are Ca-stearate, Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.
• Examples of an inorganic salt of Ca are CaO and Ca(OH) 2 .
• the organic salt of zinc or magnesium defined in component (C) is preferably a compound of the formula MeL 2 in which Me is zinc or magnesium and L is an anion of an organic acid or of an enol.
• the organic acid can, for example, be a sulfonic acid, sulfinic acid, phosphonic acid or phosphinic acid, but is preferably a carboxylic acid.
• the acid can be aliphatic, aromatic, araliphatic or cycloaliphatic; it can be linear or branched; it can be substituted by hydroxyl or alkoxy groups; it can be saturated or unsaturated and it preferably contains 1 to 24 carbon atoms.
• Examples of carboxylic acids of this type are formic, acetic, propionic, butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic, capric, lauric, palmitic, stearic, behenic, oleic, lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic, 4-butylbenzoic, toluic, 4-dodecylbenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic, 4-butylcyclohexanecarboxylic or cyclohexylacetic acid.
• the carboxylic acid can also be a technical mixture of carboxylic acids, for example technical mixtures of fatty acids or mixtures of alkylated benzoic acids.
• organic acids containing sulfur or phosphorus are methanesulfonic, ethanesulfonic, ⁇ , ⁇ -dimethylethanesulfonic, n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic, 4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethyl phenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acid or diphenylphosphinic acid.
• L is an enolate anion, it is preferably an anion of a ⁇ -dicarbonyl compound or of an o-acylphenol.
• ⁇ -dicarbonyl compounds are acetylacetone, benzoylacetone, dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl acetoacetate or ⁇ -acetylcyclohexanone.
• o-acylphenols are 2-acetylphenol, 2-butyroylphenol, 2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde.
• the enolate is preferably the anion of a ⁇ -dicarbonyl compound having 5 to 20 carbon atoms.
• Organic salts of zinc or magnesium are preferably an acetylacetonate or an aliphatic monocarboxylate having, for example, 1 to 24 carbon atoms.
• Magnesium acetate, laurate and stearate, zinc formate, acetate, oenanthate, laurate and stearate as well as zinc acetylacetonate and magnesium acetylacetonate are some of the particular preferred examples.
• Zinc stearate, magnesium stearate, zinc laurate, magnesium laurate, zinc acetylacetonate, magnesium acetylacetonate, zinc acetate and magnesium acetate are of special interest.
• the inorganic salt of zinc or magnesium is for example zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, or a carbonate containing compound such as
• the natural hydrotalcite is held to possess a structure Mg 6 Al 2 (OH) 16 CO 3 ⁇ 4 H 2 O.
• a typical empirical formula of a synthetic hydrotalcite is
• Examples of the synthetic product include:
• Preferred synthetic hydrotalcites are L-55R®II from ®REHEIS as well as ®ZHT-4A and ®DHT-4A from ®Kyowa Chemical Industry Co.
• a preferred embodiment of this invention relates to a stabilizer mixture wherein component (C) is hydrotalcite, dolomite, Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide, Zn-hydroxide, Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate, Mg-laurate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate or Mg-acetate.
• component (C) is hydrotalcite, dolomite, Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide, Zn-hydroxide, Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate, Mg-laurate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-a
• a further preferred embodiment of this invention relates to a stabilizer mixture containing additionally
• the pigment (component (D1)) 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 component (D2)
• examples of the UV absorber are 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′-octy
• the 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 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-methoxycinnamate, 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-
• the monobenzoate of resorcinol 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 the present invention is useful for stabilizing polyolefins against degradation induced by light, heat or oxidation.
• suitable polyolefins are shown in 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), branched low density polyethylene (BLDPE).
• 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 low density polyethylene
• LLDPE linear low density
• 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:
• 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 copolymers and their salts
• the invention therefore also relates to a composition containing a polyolefin and the stabilizer mixture as described herein and to a method for stabilizing a polyolefin against degradation induced by light, heat or oxidation, which comprises incorporating into the polyolefin the stabilizer mixture.
• polystyrene resin polystyrene resin
• polyethylene and polypropylene as well as a polyethylene copolymer or a polypropylene copolymer are particularly preferred.
• the invention furthermore relates to a composition comprising a polyolefin and a stabilizer mixture containing
• component (A) of the stabilizer mixture is the compound 96-I, 96-II or 100-A.
• the components (A), (B), (C) and optionally (D1) and/or (D2) may be added to the polyolefin either individually or mixed with one another.
• the sterically hindered amine compound (component (A)) is present in the polyolefin in an amount of preferably 0.01 to 5%, in particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the polyolefin.
• the organic or inorganic salt of Ca (component (B)) is present in the polyolefin in an amount of preferably 0.005 to 5%, in particular 0.02 to 0.5%, relative to the weight of the polyolefin.
• the organic or inorganic salt of Zn or Mg (component (C)) is present in the polyolefin in an amount of preferably 0.01 to 5%, in particular 0.05 to 0.5%, relative to the weight of the polyolefin.
• the pigment (component (D1)) is optionally present in the polyolefin in an amount of preferably 0.01 to 10%, in particular 0.05 to 1%, relative to the weight of the polyolefin.
• the UV absorber (component (D2)) is optionally present in the polyolefin in an amount of preferably 0.01 to 1%, in particular 0.05 to 0.5%, relative to the weight of the polyolefin.
• the total amount of component (D3) (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 the components (A):(B) is preferably 20:1 to 1:5.
• the weight ratio of the components (A):(C) is preferably 20:1 to 1:5.
• the weight ratio of the components (A):(D1) is preferably 10:1 to 1:10.
• the weight ratio of the components (A):(D2) is preferably 20:1 to 1:2.
• the weight ratio of the components (A):(D3) is preferably 10:1 to 1:10.
• the above components can be incorporated into the polyolefin by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the polyolefin, if necessary with subsequent evaporation of the solvent.
• the components can be added to the polyolefin 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 (A), (B), (C) and optionally (D1) and/or (D2) can be melt blended with each other before incorporation in the polyolefin. They can be added to the polyolefin before or during the polymerization or before the crosslinking.
• polyolefin 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 putties.
• the stabilized polyolefin may additionally also contain various conventional additives, for example:
• Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-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-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
• Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
• 2,6-di-tert-butyl-4-methoxyphenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
• Hydroxylated thiodiphenyl ethers for example 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.
• 2,2′-thiobis(6-tert-butyl-4-methylphenol 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis-(3,6-di-sec-amylphenol), 4,4′-bis-(2,
• Alkylidenebisphenols for example 2,2′-methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclohexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-( ⁇ , ⁇ -dimethylbenzyl)-4-isobutylphenol
• 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)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
• 1.8. Hydroxybenzvlated 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.
• hydroxybenzvlated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-
• 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-hydroxyphenyl)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-trio
• esters of D-(5-tert-butyl-4-hydroxy-3-methylphenyl)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-trioxabi
• esters of ⁇ -(3,5-dicyclohexyl-4-hydroxyphenyl)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]octane.
• esters of 3,5-di-tert-butyl-4-hydroxyphenyl 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-cyclohexyldiethanolamine, nickel dibutyidithiocarbamate, 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-cyclohexyldiethanolamine, nickel dibutyidithio
• 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 phosphonites 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 diphosphite, diis
• Hydroxylamines for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhy-droxylamine, 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.
• [0401] is one of the preferred conventional additives which may additionally be incorporated into the polyolefin to be stabilized.
• the weight ratio of the total amount of components (A), (B), (C) and optionally (D1) and/or (D2) to the total amount of the conventional additives can be, for example, 100:1 to 1:100.
• the plaques are mounted on sample holders and subjected to natural weathering in Florida (45° South, direct, approximately 140 kLy/year). Periodically, the carbonyl content of the samples is measured with an infrared spectrophotometer. The exposure time corresponding to formation of a carbonyl absorbance of 0.5 is a measure for the efficiency of the stabilizer system.
• the synergistic effect of the two coadditivs is determined by a comparison of the calculated T 0.5 value with the actually measured T 0.5 value.
• the T 0.5 values are calculated on the basis of the additivity law (B. Ranby and J. F.
• the tapes are mounted without tension on sample holders and exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63 ⁇ 2° C., without water-spraying). Periodically, the tensile strength of the exposed tapes is measured. The exposure time corresponding to a loss of 50% (T 50 ) of the initial tensile strength is a measure for the efficiency of the stabilizer system.

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• Compositions Of Macromolecular Compounds (AREA)
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• 1998
  • 1998-12-14 US US09/211,198 patent/US20020016390A1/en not_active Abandoned
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