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WO2011117266A1 - Compositions ignifuges à base de sels d'acides phosphiniques et de dérivés de nitroxyle - Google Patents

Compositions ignifuges à base de sels d'acides phosphiniques et de dérivés de nitroxyle Download PDF

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WO2011117266A1
WO2011117266A1 PCT/EP2011/054387 EP2011054387W WO2011117266A1 WO 2011117266 A1 WO2011117266 A1 WO 2011117266A1 EP 2011054387 W EP2011054387 W EP 2011054387W WO 2011117266 A1 WO2011117266 A1 WO 2011117266A1
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alkyl
bis
tetramethylpiperidin
hydroxy
crc
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Rainer Xalter
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BASF SE
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BASF SE
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Priority to KR1020127027987A priority Critical patent/KR20120135428A/ko
Priority to JP2013500478A priority patent/JP5615425B2/ja
Priority to EP11709427A priority patent/EP2550321A1/fr
Priority to CN2011800153548A priority patent/CN102834445A/zh
Priority to KR20157001653A priority patent/KR20150024901A/ko
Priority to BR112012023783A priority patent/BR112012023783A2/pt
Priority to RU2012145171/04A priority patent/RU2012145171A/ru
Publication of WO2011117266A1 publication Critical patent/WO2011117266A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • 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
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/32—Compounds containing nitrogen bound to 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/84—Flame-proofing or flame-retarding additives

Definitions

  • the present invention relates to flame retardant polymer compositions which comprise phosphinic acid salts in combination with so-called sterically hindered nitroxyl derivatives.
  • the compositions are especially useful for the manufacture of flame retardant compositions based on thermoplastic polymers, especially polyolefin homo- and co- polymers and copolymers with vinyl monomers.
  • Flame retardants are added to polymeric materials (synthetic or natural) to enhance the flame retardant properties of the polymers. Depending on their composition, flame retardants may act in the solid, liquid or gas phase either chemically, e.g. as a spumes- cent by liberation of nitrogen, and/or physically, e.g. by producing a foam coverage. Flame retardants interfere during a particular stage of the combustion process, e.g. during heating, decomposition, ignition or flame spread.
  • polymer compositions with excellent flame retardant properties are prepared in the event that phosphinic acid salts in combination with so-called sterically hindered amines are added to the polymer substrate.
  • the invention relates to a composition, particularly a flame retardant composition, which comprises a) A salt of a phosphinic acid as represented by the structural formulae o O o
  • R 1 and R 2 represents hydrogen or CrC 8 alkyl; or both R 1 and R 2 represent CrC 8 alkyl; and
  • R 3 represents CrCi 0 alkylene, C 2 -Ci 0 alkylene interrupted by phenylene, phenylene, (Ci-C 4 alkyl) 1-3 phenylene, or phenyl-Ci-C 4 alkylene; b) A tetraalkylpiperidine or tetraalkylpiperazine derivative selected from the
  • composition defined above for use as a flame retardant is another embodiment of the invention.
  • a preferred embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises
  • 2,2,6,6-tetraalkylpiperidine-1 -oxides 1 -hydroxy-2,2,6,6-tetraalkylpiperidines, 1 -alkoxy-2,2,6,6-tetraalkylpiperidines and 1 -acyloxy-2,2,6,6-piperidines; and c) A thermoplastic polymer substrate.
  • compositions according to the invention exhibit excellent flame retardant properties at low concentrations of the components a) and b).
  • composition as defined above, comprises the following components: Component a)
  • phosphinic acid also comprises within its scope the tautomeric form HP(OH) 2 , wherein the hydrogen atom which is directly attached to the phosphorus atom is substituted by organic substituents, such as CrC 8 alkyl.
  • salt of phosphinic acid comprises within its scope preferably a metal salt, for example an alkali metal or alkaline earth metal salt, e.g. the sodium, potassium, mag- nesium or calcium salt or the iron(ll), iron(lll), zinc or boron salt.
  • a metal salt for example an alkali metal or alkaline earth metal salt, e.g. the sodium, potassium, mag- nesium or calcium salt or the iron(ll), iron(lll), zinc or boron salt.
  • R 1 and R 2 defined as CrC 8 alkyl is straight or, where possible branched CrC 8 alkyl and is for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl or 2-ethylhexyl.
  • R 3 defined as CrCi 0 alkylene is straight chain or, where possible branched
  • Ci-Ci 0 alkylene e.g. methylene, ethylene, 1 ,2- or 1 ,3- propylene or 1 ,2-, 1 ,3- or
  • R 3 defined as C 2 -Ci 0 alkylene interrupted by phenylene is, for example a bivalent group of the partial formulae , or , wherein the dotted lines point to the carbon atom of attachment.
  • R 3 defined as phenylene is 1 ,2-, 1 ,3- or 1 ,4-phenylene.
  • R 3 defined as (Ci-C 4 alkyl) 1-3 phenylene is, for example, 1 ,2-, 1 ,3- or 1 ,4-phenylene substituted by 1 -3 methyl or ethyl groups.
  • R 3 defined as phenyl-Ci-C 4 alkylene is, for example, one of the above-mentioned Ci-C 8 alkyl groups substituted by phenyl.
  • the composition comprises the aluminium salt of diethylphosphinic acid.
  • the term salt comprises non-metallic salts, e.g. the acid addition salts obtainable by reaction of phosphinic acid with ammonia, amines or amides, e.g. the (C C 4 alkyl) 4 N + , (CrC 4 alkyl) 3 NH + , (C 2 -C 4 alkylOH) 4 N + , (C 2 -C 4 alkylOH) 3 NH + , (C 2 -C 4 alkylOH) 2 N(CH 3 ) 2 + , (C 2 -C 4 alkylOH) 2 NHCH 3 + , (C 6 H 5 ) 4 N + , (C 6 H 5 ) 3 NH + , (C 6 H 5 CH 3 ) 4 N + , (C 6 H 5 CH 3 ) 3 NH + , NH 4 + , melamine or guanidine salt.
  • non-metallic salts e.g. the acid addition salts obtainable by reaction of phosphin
  • the ammonium, (Ci-C 4 alkyl) 1-4 ammonium or (2-hydroxy- ethyl) 1-4 ammonium, e.g. tetramethylammonium, tetraethylammonium, the 2-hydro- xyethyltrimethylammonium, melamine or guanidine salt are particularly preferred.
  • the salt of a phosphinic acid (I) is represented by the formula
  • R 1 and R 2 represents hydrogen or CrC 8 alkyl; or both R 1 and R 2 represent
  • M represents (Ci-C 4 alkyl) 4 N, (C C 4 alkyl) 3 NH, (C 2 -C 4 alkylOH) 4 N, (C 2 -C 4 alkylOH) 3 NH, (C 2 -C 4 alkylOH) 2 N(CH 3 ) 2! (C 2 -C 4 alkylOH) 2 NHCH 3 , (C 6 H 5 ) 4 N, (C 6 H 5 ) 3 NH, (C 6 H 5 CH 3 ) 4 N, (C 6 H 5 CH 3 ) 3 NH, NH 4 , melamine, guanidine, an alkali metal or earth alkali metal ion, or an aluminium, zinc, iron or boron ion;
  • n is a numeral from 1 -3 and indicates the number of positive charges on M; and n is a numeral from 1 -3 and indicates the number of phosphinic acid anions corresponding to M m+ .
  • the salt of a phosphinic acid (I) of Component a) is represented by the formula
  • Component a) is preferably contained in the flame retardant compositions according to the invention in an amount from 0.1 - 45.0 wt.%, preferably 1 - 30.0 wt.%, based on the weight of the polymer substrate component c), and component b) is preferably con- tained in an amount from 0.05 - 5.0 wt.%, preferably 0.1 - 2.0 wt.%.
  • the preferred ratio of components a) : b) is in the range 50 : 1 - 1 : 5, preferably 20 : 1 - 1 : 2.
  • a further embodiment of the invention relates to a mixture, which comprises
  • R 1 and R 2 represents hydrogen or CrC 8 alkyl; or both R 1 and R 2 represent CrC 8 alkyl; and R 3 represents CrCi 0 alkylene, C 2 -Ci 0 alkylene interrupted by phenylene, phenylene, (Ci-C 4 alkyl) 1-3 phenylene, or phenyl-CrC 4 alkylene; and b) A tetraalkylpiperidine derivative selected from the group that consists of
  • 2,2,6,6-tetraalkylpiperidine-1 -oxides 1 -hydroxy-2,2,6,6-tetraalkylpiperidines, 1 -alkoxy-2,2,6,6-tetraalkylpiperidines and 1 -acyloxy-2,2,6,6-piperidines.
  • the mixture is useful for imparting flame retardancy to a polymer substrate.
  • a further embodiment of the invention relates to a process for imparting flame retardancy to a polymer substrate, which process comprises adding to a polymer substrate of component c) the above defined mixture of components a) and b).
  • a suitable tetraalkylpiperidine or tetralkylpiperazine derivative is selected from the group that consists of 2,2,6, 6-tetraalkylpiperidine-1 -oxides, 1 -hydroxy-2,2,6,6-tetra- alkylpiperidines, 1 -alkoxy-2,2,6,6-tetraalkylpiperidines, 1 -acyloxy-2,2,6,6-piperidines, 1 - hydroxy-2,2,6,6-tetraalkylpiperazines, 1 -alkoxy-2,2,6,6-tetraalkylpiperazines, and 1 -acyloxy-2,2,6,6-piperazines.
  • R R 4 represent CrC 4 alkyl, preferably methyl or ethyl.
  • one of Ri and R 2 and one of R 3 of R 4 represents ethyl and the other ones represent methyl or all of R R 4 represent methyl;
  • E represents hydrogen, CrC 2 oalkyl, C 5 -C 6 cycloalkyl or C 2 -C 2 oalkyl, C 5 -C 6 cycloalkyl or C 2 -C 20 alkenyl with additional substituents; or represents the acyl group of a
  • Ci-C 20 monocarboxylic or C 2 -C 20 dicarboxylic acid Ci-C 20 monocarboxylic or C 2 -C 20 dicarboxylic acid.
  • one of the dotted lines in 4- position of the piperidine represents a bond to hydrogen or an N-substituent and the other one represents a bond to an O-substituent or a C-substituent.
  • both dotted lines in 4-position of the piperidine represent bonds to hydrogen, O-substituents or C-substituents or represent a double bond to oxygen.
  • the nitrogen in 4-position of the piperazine is bonded to hydrogen or carbon-substituents.
  • E represents hydrogen, CrC 2 oalkyl, C 5 -C 6 cycloalkyl or C 2 -C 2 oalkyl, C 5 -C 6 cycloalkyl or C 2 -C 2 oalkenyl with additional substituents; or represents the acyl group of a Ci-C 2 omonocarboxylic or C 2 -C 2 oclicarboxylic acid; or, in the alternative, the group >N-0-E is replaced with the group >N-0.
  • Alkyl is straight or branched and 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.
  • Cycloalkyl groups include cyclopentyl and cyclohexyl; typical cycloalkenyl groups include cyclohexenyl; while typical aralkyl groups include benzyl, alpha-methyl-benzyl, alpha, alpha-dimethylbenzyl or phenethyl.
  • E defined as the acyl group of a C 2 -C 20 dicarboxylic acid is, for example, the diacyl radi- cal derived from a monobasic organic acid having C radicals and two acid functions, e.g. a diacyl radical derived from an aliphatic, aromatic or cycloaliphatic dicarboxylic acid.
  • Suitable aliphatic dicarboxylic acids have from 2 to 40 C-atoms, e.g. oxalic acid, malo- nic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, azelaic acid and dimeric acid (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acids, e.g. octadecylsuccinic acid.
  • Suitable cycloaliphatic dicarboxylic acids are, for example, 1 ,3-cyclobutanedicarboxylic acid, 1 ,3-cyclopentanedicarboxylic acid, 1 ,3- and 1 ,4-cyclohexanedicarboxylic acid, 1 ,3- and 1 ,4-(dicarboxymethyl)cyclohexane or 4,4'-dicyclohexyldicarboxylic acid.
  • Preferred members of this group include the acyl radical of oxalic acid, adipic acid, succinic acid, suberic acid, sebacic acid, phthalic acid dibutylmalonic acid, dibenzyl- malonic acid or butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid, or bicyclohep- tenedicarboxylic acid, with succinates, sebacates, phthalates and isophthalates being specific examples.
  • E is a divalent acyl radical of a dicarbamic acid, it is for example an acyl radical of hexamethylenedicarbamic acid or of 2,4-toluylenedicarbamic acid;
  • T is a straight or branched chain alkylene of 1 to 18 C-atoms, cycloalkylene of 5 to 18 C-atoms, cycloalkenylene of 5 to 18 C-atoms, a straight or branched chain alkylene of 1 to 4 C-atoms substituted by phenyl or by phenyl substituted by one or two alkyl groups of 1 to 4 C-atoms;
  • b is 1 , 2 or 3 with the proviso that b does not exceed the number of C-atoms in T, and when b is 2 or 3, each hydroxyl group is attached to a different C-atoms of T;
  • R is hydrogen or methyl
  • m 1 to 4.
  • R 2 is hydrogen, CrCi 8 alkyl or said alkyl optionally interrupted by one or more oxygen atoms, C 2 -Ci 2 alkenyl, C 6 -Ci 0 aryl, C 7 -Ci 8 aralkyl, glycidyl, the monovalent acyl radical of an aliphatic, cycloaliphatic or aromatic carboxylic acid, or a carbamic acid, for example an acyl radical of an aliphatic carboxylic acid having 2-18 C-atoms, of a cycloaliphatic carboxylic acid having 5-12 C-atoms or of an aromatic carboxylic acid having 7-15 C- atoms, or represents groups of the partial formulae
  • R 2 is CrCi 2 alkylene, C 4 -Ci 2 alkenylene, xylylene, a divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid or of a dicarbamic acid, for example an acyl radical of an aliphatic dicarboxylic acid having 2-18 C-atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C-atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C-atoms;
  • D-i and D 2 are independently hydrogen, CrC 8 alkyl, aryl or aralkyi including the 3,5-di-t- butyl-4-hydroxybenzyl radical;
  • D 3 is hydrogen, CrCi 8 alkyl or CrC 2 oalkenyl
  • d is 0-20;
  • R 2 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid
  • R 2 is a tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetra- carboxylic acid including 1 ,2,3,4-butanetetracarboxylic acid, 1 ,2,3,4-but-2-enetetra- carboxylic, and 1 ,2,3,5- and 1 ,2,4,5-pentanetetracarboxylic acid;
  • variable p 1 , 2 or 3
  • R 3 is hydrogen, Ci-Ci 2 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 9 aralkyl, C 2 -Ci 8 alkanoyl, C 3 - C 5 alkenoyl or benzoyl;
  • R 4 is hydrogen, CrCi 8 alkyl, C 5 -C 7 cycloalkyl, C 2 -C 8 alkenyl, unsubstituted or substituted by cyano, carbonyl or carbamide, or is aryl, aralkyi, or glycidyl, a group of the partial formula -CH 2 -CH(OH)-Z or of the partial formulae -CO-Z or -CONH-Z, wherein Z is hydrogen, methyl or phenyl, or represents groups of the partial formulae
  • h is 0 or 1 ;
  • R 3 and R 4 together, when p is 1 , represents alkylene of 4 to 6 C-atoms, or 2-oxo-polyal- kylene, or the cyclic acyl radical of an aliphatic or aromatic 1 ,2- or 1 ,3-dicarboxylic acid; When p is 2,
  • R 4 is a direct bond or is d-C ⁇ alkylene, C 6 -Ci 2 arylene, xylylene, a -CH 2 CH(OH)-CH 2 group or a group of the partial formula -CH2-CH(OH)-CH 2 -0-X-0-CH2-CH(OH)-CH 2 -, wherein X is C 2 -Ci 0 alkylene, C 6 -Ci 5 arylene or C 6 -Ci 2 cycloalkylene; or, provided that R 3 is other than alkanoyl, alkenoyl or benzoyl, R 4 additionally represents the divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or represents the group -CO-; or
  • R 4 represents a group of the partial formula
  • T 8 and T 9 are independently hydrogen, CrCi 8 alkyl, or T 8 and T 9 together repre- sent C 4 -C 8 alkylene or 3-oxapentamethylene, for instance T 8 and T 9 together are 3- oxapentamethylene;
  • R 4 is 2,4,6-triazinyl
  • n 1 or 2;
  • R 5 and R' 5 are independently Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, C 7 -Ci 2 aralkyl, or R 5 additionally represents hydrogen, or R 5 and R' 5 together are C 2 -C 8 alkylene or hydroxyalkylene or C 4 -C 24 acyloxyalkylene;
  • R 5 and R' 5 together are a group of the partial formula (-CH 2 ) 2 C(CH 2 -) 2 ;
  • R 6 is hydrogen, d-C ⁇ alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl; or
  • R 7 is hydrogen, d-C ⁇ alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 2 -C 4 hydroxy- alkyl, C 2 -C 6 alkoxyalkyl, C 6 -Ci 0 aryl, glycidyl, a group of the partial formula
  • R 7 is C 2 -Ci 2 alkylene, C 6 -Ci 2 arylene, a group of the partial formula
  • X is C 2 -Ci 0 alkylene, C 6 -Ci 5 arylene or C 6 -Ci 2 cycloalkylene, or a group of the partial formula
  • Z' is hydrogen, CrCi 8 alkyl, allyl, benzyl, C 2 -Ci 2 alkanoyl or benzoyl;
  • Qi is -N(R 8 )- or -0-;
  • E 7 is Ci-C 3 alkylene, the group -CH 2 -CH(R 9 )-0- wherein R 9 is hy- drogen, methyl or phenyl, the group -(CH 2 ) 3 -NH- or a direct bond;
  • Rio is hydrogen or C Ci 8 alkyl
  • R 8 is hydrogen, Ci-Ci 8 alkyl, C 5 -C 7 cycloalkyl, C 7 - Ci 2 aralkyl, cyanoethyl, C 6 -Cioaryl, the group -CH 2 -CH(R 9 )-OH wherein R 9 has the meaning defined above; or represents groups of the partial formulae
  • G 4 is C 2 -C 6 alkylene or C 6 -Ci 2 arylene; or R 8 is a group of the partial formula
  • Formula F denotes a recurring structural unit of a polymer where T 3 is ethylene or 1 ,2- propylene, is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; for example a copolymer of ethylene and ethyl acry- late, and where k is 2 to 100;
  • T 4 has the same meaning as R 4 when p is 1 or 2;
  • T 5 is methyl
  • T 6 is methyl or ethyl, or T 5 and T 6 together are tetramethylene or pentamethylene, for instance T 5 and T 6 are each methyl;
  • M and Y are independently methylene or carbonyl, and T 4 is ethylene where n is 2;
  • T 7 is as defined as R 7 , and T 7 is for example octamethylene where n is 2;
  • Tio and Tii are independently alkylene of 2 to 12 C-atoms; or Tn represents a group of the partial formula
  • T T piperazinyl or represents groups of the partial formulae
  • Rn is as defined as R 3 or additionally represents a group of the partial formula
  • a, b and c are independently 2 or 3, and f is 0 or 1 , for instance a and c are each 3, b is 2 and f is 1 ;
  • e is 2, 3 or 4, for example 4;
  • T-I3 is the same as R 2 with the proviso that T 13 is other than hydrogen when n is 1 ;
  • Ei and E 2 being different, each are -CO- or -N(E 5 )- where E 5 is hydrogen, d-C ⁇ alkyl or C 4 -C 24 alkoxycarbonylalkyl, for instance Ei is -CO- and E 2 is -N(E 5 )-;
  • E 3 is hydrogen, CrC 3 oalkyl, phenyl, naphthyl, said phenyl or said naphthyl substituted by chlorine or by Ci-C 4 alkyl, or C 7 -Ci 2 phenylalkyl, or said phenylalkyl substituted by Ci-C 4 alkyl of 1 to 4 C-atoms;
  • E 4 is hydrogen, alkyl of 1 to 30 C-atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 C- atoms, or E 3 and E 4 together are polymethylene of 4 to 17 C-atoms, or said polymethylene substituted by up to four d-C 4 alkyl groups, for example methyl;
  • E 6 is an aliphatic or aromatic tetravalent radical
  • R 2 of formula (N) is a previously defined when m is 1 ;
  • Gi a direct bond, C 1 -C 12 alkylene, phenylene or -NH-G'-NH wherein G' is C 1 -C 12 al- kylene.
  • Suitable tetraalkylpiperidine or tetralkylpiperazine derivatives are, for example, compounds of the formulae 1 -12:
  • E 2 , E 3 and E 4 are independently CrC 4 alkyl, or Ei and E 2 are independently
  • Ri is CrCi 8 alkyl, C 5 -Ci 2 cycloalkyl, a bicyclic or tricyclic hydrocarbon radical of 7 to 12 carbon atoms, C 7 -Ci 5 phenylalkyl, C 6 -Ci 0 aryl or said aryl substituted by one to three Ci-C 8 alkyl;
  • R 2 is hydrogen or a linear or branched chain C Ci 2 alkyl
  • R 3 is alkylene of 1 to 8 carbon atoms, or R 3 is -CO-, -CO-R4-, -CONR 2 -, or -CO-NR 2 -R 4 ; R 4 is Ci-C 8 alkylene;
  • R 5 is hydrogen, linear or branched chain Ci-Ci 2 alkyl, or represents a group of the partial formula
  • R 4 when R 4 is ethylene, two R 5 methyl substituents can be linked by a direct bond with the triazine bridging group -N(R 5 )-R 4 -N(R 5 )- forming a piperazin-1 ,4-diyl group;
  • R 6 is C 2 -C 8 alkylene or represents a group of the partial formula
  • A is -O- or -IMR 7 - where R 7 is hydrogen, straight or branched chain Ci-Ci 2 alkyl; or R 7 is a group of the partial formula
  • T is phenoxy, phenoxy substituted by one or two Ci-C 8 alkyl or Ci-C 8 alkoxy or -N(R 2 ) 2 with the stipulation that R 2 is other than hydrogen; or T is a group of the partial formula
  • X is -IMH2, -NCO, -OH, -O-glycidyl, or -NHNH 2 , and
  • Y is -OH, -IMH2, -NHR 2 where R 2 is other than hydrogen; or Y is -NCO, -COOH, oxiranyl, -O-glycidyl, or -Si(OR 2 )3;
  • R 3 -Y- is -CH 2 CH(OH)R 2 where R 2 is alkyi or said alkyi interrupted by one to four oxygen atoms, or R 3 -Y- is -CH 2 OR 2 ; or
  • the hindered amine compound is a mixture of N,N',N"'-tris ⁇ 2,4-bis[(1 -hydro- carbyloxy-2,2,6,6-tetramethylpiperidin-4-yl)alkylamino]-s-triazin-6-yl ⁇ -3,3'-ethylene- diiminodipropylamine; N,N',N"-tris ⁇ 2,4-bis[(1 -hydrocarbyloxy-2,2,6,6-tetramethyl- piperidin-4-yl)alkylamino]-s-triazin-6-yl ⁇ -3,3'-ethylenediiminodipropylamine, and bridged derivatives as described by formulae
  • Ri and R 2 are the s-triazine moiety E; and one of R 3 and R 4 is the s-triazine moiety E with the other ones of R 3 or R 4 being hydrogen;
  • R is methyl, propyl, cyclohexyl or octyl, for instance cyclohexyl;
  • R 5 is Ci-Ci 2 alkyl, for example n-butyl
  • E-i is a gro
  • the group E-i can have both termini in the same tetraamine T as in formula 15, where two of the E moieties of the tetraamine are replaced by one E-i group; or
  • All three s-triazine substituents of tetraamine T can be E-i such that one E-i links T and T-i and a second E-i has both termini in tetraamine T;
  • L is propanediyl, cyclohexanediyl or octanediyl
  • G, Gi and G 2 are each tetraamines substituted by RrR 4 as defined for formula I, except that G and G 2 each have one of the s-triazine moieties E replaced by E-i, and Gi has two of the triazine moieties E replaced by E-i, so that there is a bridge between G and Gi and a second bridge between Gi and G 2 ;
  • hindered amine is a compound of the formula (17)
  • index n ranges from 1 to 15;
  • Ri2 is C 2 -Ci2alkylene, C 4 -Ci 2 alkenylene, C 5 -C 7 cycloalkylene, C 5 -C 7 cycloalkylene-di(Cr C 4 alkylene), Ci-C 4 alkylene-di(C5-C 7 cycloalkylene), phenylene-di(CrC 4 alkylene) or C 4 -Ci 2 alkylene interrupted by 1 ,4-piperazinediyl, -O- or >N-X-i with being d-C ⁇ acyl or
  • R 12 is a group of the partial formulae:
  • X 2 being CrCi 8 alkyl, C 5 -Ci 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 CrC 4 alkyl; phenyl which is unsubstituted or substituted by 1 , 2 or 3 CrC 4 alkyl or CrC 4 alkoxy; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 C C 4 alkyl; and
  • radicals X 3 being independently of one another C 2 -Ci 2 alkylene
  • Ri 3 , Ri4 and Ri 5 which are identical or different, are hydrogen, CrCi 8 alkyl,
  • C 5 -Ci 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 CrC 4 alkyl; C 3 -Ci 8 alk- enyl, phenyl which is unsubstituted or substituted by 1 , 2 or 3 CrC 4 alkyl or CrC 4 alk- oxy; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC 4 alkyl; tetrahydrofurfuryl or
  • Y N - with Y being -0-, -CH 2 -, -CH 2 CH 2 - or >N-CH 3 , or -N(R 14 )(Ri 5 ) is additionally the group Y
  • the radicals A are independently of one another -ORi 3 , -N(R 14 )(R 15 ) or a group of the partial formula:
  • X is -O- or >N-R 16 ;
  • Ri 6 is hydrogen, CrCi 8 alkyl, C 3 -Ci 8 alkenyl, C 5 -Ci 2 cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 CrC 4 alkyl; C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC 4 alkyl; tetrahydrofurfuryl, a group of the partial formula:
  • R11 has one of the definitions given for R 16 ;
  • radicals B have independently of one another one of the definitions given for A.
  • tetraalkylpiperidine and tetraalkylpiperazine compounds are known in the art, also known as N-alkoxy hindered amines and NOR-hindered amines or NOR-hindered amine light stabilizers or NOR-HALS, such as the ones disclosed in U.S. Pat. Spec. Nos. 5,004, 770, 5,204,473, 5,096,950, 5,300,544, 5, 112,890, 5, 124,378, 5, 145,893, 5,216, 156, 5,844,026, 6, 117,995 or 6,271 ,377.
  • Hindered hydroxyalkoxyamine stabilizers are also known as N- hydroxyalkoxy hindered amines, or NORol-HALS.
  • Re resentative structures are the following:
  • R and R' include N-, O- or C-substituents.
  • the compounds are hydroxylamine esters.
  • the hydroxylamines are reacted with an acid derivative to form the final hydroxylamine ester.
  • Such esterification processes are known and described in the literature.
  • the tetraalkylpiperidine derivative is selected from the group of 2,2,6, 6-tetraalk lpiperidine-1 -oxides of the formula
  • R a and R b represents
  • Both R a and R b represent hydrogen, O-substituents or C-substituents;
  • R represents CrC 2 oalkyl, C 5 -C 6 cycloalkyl or C 2 -C 2 oalkyl, C 5 -C 6 cycloalkyl or C 2 -C 2 oalkenyl with additional substituents;
  • Ac represents the acyl group of a Ci-C 20 monocarboxylic or Ci-C 20 dicarboxylic acid
  • R1-R4 each represent CrC 4 alkyl
  • R 5 and R 6 independently of one another, represent hydrogen or a substituent se- lected from the group consisting of CrC 4 -alkyl, CrC 3 alkylphenyl and phenyl;
  • R 5 and R 6 together represent oxo.
  • the composition comprises as Component b) at least one tetraalkylpiperidine derivative III a, III b, III c or III d,
  • R a and R b represents
  • Both R a and R b represent hydrogen, O-substituents or C-substituents;
  • R represents CrC 8 alkyl, C 5 -C 6 cycloalkyl or C 2 -C 8 alkyl, C 5 -C 6 cycloalkyl or C 2 -C 8 alkenyl with additional substituents;
  • Ac represents the acyl group of a Ci-C 8 carboxylic acid; and R1-R4 are each methyl; and
  • R 5 and R 6 each represent hydrogen.
  • the composition comprises as Component b) at least one tetraalkylpiperidine derivative III a, III b, III c or III d,
  • R a and R b represents
  • Both R a and R b represent O-substituents or C-substituents
  • R represents CrC 8 alkyl, C 5 -C 6 cycloalkyl or C 2 -C 8 alkyl, C 5 -C 6 cycloalkyl or C 2 -C 8 alkenyl substituted by hydroxy;
  • Ac represents the acyl group of a Ci-C 8 carboxylic acid
  • R1-R4 are each methyl
  • R 5 and R 6 each represent hydrogen.
  • Component b) consists of at least one tetraalkylpiperidine derivative III c or III d selected from the group consisting of
  • the oligomeric compound which is the condensation product of 4,4'-hexame- thylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1 -cyclo- hexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,
  • n is from 1 to 15 (Flamestab NOR 1 16®).
  • polymer substrate comprises within its scope thermoplastic polymers or thermosets.
  • thermoplastic polymers A list of suitable thermoplastic polymers is given below:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1 -ene, poly-4-methylpent-1 -ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be cross linked), for example high density polymethylene (HDPE), high density and high molecular weight polyethyl- ene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene
  • HDPE high density polymethylene
  • HDPE-HMW high density and high molecular weight polyethyl- ene
  • HDPE-UHMW medium density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • VLDPE linear low density polyethylene
  • ULDPE ULDPE
  • 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:
  • Catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table.
  • These metals usu- ally have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either a- or o-bond coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) 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 la, I la and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, and amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler-Natta),
  • TNZ DuPont
  • SSC single site catalysts
  • LDPE/HDPE LDPE/HDPE
  • 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, ethyl- ene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propyl- ene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclo- hexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacry- late copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethylene-propylene copolymers,
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • the homopolymers and copolymers mentioned above may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred.
  • Stereo block polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly(a-methylstyrene).
  • Homopolymers and copolymers may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred.
  • Stereo block polymers are also included; a) Copolymers including aforementioned vinyl aromatic monomers and co- monomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylo- nitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, sty- rene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, sty- rene/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
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvi- nylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvi- nylcyclohexane
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a Homopolymers and copolymers may have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereo block polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or omethylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybu- tadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers;
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulphochlorinated 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.
  • Polymers derived from ⁇ , ⁇ -unsaturated acids and derivatives thereof such as poly- acrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acryloni- trile/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.
  • Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, poly- ethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes, which contain ethylene oxide as a co-monomer; polyacetals modified with thermoplastic poly- urethanes, acrylates or MBS.
  • Polyamides and co-polyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example poly- amide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 1 1 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and tereph- thalic 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
  • Polyureas Polyimides, polyamide imides, polyether imides, polyester imides, poly- hydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, poly- butylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block co-polyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Blends of the aforementioned polymers for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,
  • PC/thermoplastic PUR POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers
  • PA/HDPE PA/PP
  • PA/PPO PA/PPO
  • PBT/PC/ABS PBT/PET/PC.
  • Polycarbonates are obtainable by interfacial processes or by melt processes (catalytic transesterification).
  • the polycarbonate may be either branched or linear in structure and may include any functional substituents.
  • Polycarbonate copoly- mers and polycarbonate blends are also within the scope of the invention.
  • the term polycarbonate should be interpreted as inclusive of copolymers and blends with other thermoplastics. Methods for the manufacture of polycarbonates are known, for example, from U.S. Patent Specification Nos. 3,030,331; 3, 169, 121;
  • a diphenol such as bis henol A
  • suitable diphenols are:
  • bisphenol C 0H
  • bisphenol E ⁇ 0 ⁇ t H /r 0
  • the carbonate source may be a carbonyl halide, a carbonate ester or a halofor- mate.
  • Suitable carbonate halides are phosgene or carbonylbromide.
  • Suitable carbonate esters are dialkylcarbonates, such as dimethyl- or diethylcarbonate, di- phenyl carbonate, phenyl-alkylphenylcarbonate, such as phenyl-tolylcarbonate, dialkylcarbonates, such as dimethyl- or diethylcarbonate, di-(halophenyl)carb- onates, such as di-(chlorophenyl)carbonate, di-(bromophenyl)carbonate, di- (trichlorophenyl)carbonate or di-(trichlorophenyl)carbonate, di-(alkylphenyl)car- bonates, such as di-tolylcarbonate, naphthylcarbonate, dichloronaphthylcarbonate and
  • the polymer substrate mentioned above which comprises polycarbonates or poly- carbonate blends is a polycarbonate-copolymer, wherein isophthalate/tereph- thalate-resorcinol segments are present.
  • polycarbonates are commercially available, e.g. Lexan® SLX (General Electrics Co. USA).
  • Other polymeric substrates of component b) may additionally contain in the form as admixtures or as copolymers a wide variety of synthetic polymers including polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly(meth)acrylates, thermoplastic polyure- thanes, polysulphones, polyacetals and PVC, including suitable compatibilizing agents.
  • the polymer substrate may additionally contain thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof.
  • thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers and copolymers thereof.
  • Specific embodiments include polypropylene (PP), polyethylene (PE), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), glycol-modified poly- cyclohexylenemethylene terephthalate (PCTG), polysulphone (PSU), polymethylmethacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene- styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile-ethylene- propylene-styrene
  • Epoxy resins consisting of a di- or polyfunctional epoxide compound, wherein at least two epoxy groups of the partial formula
  • Ri and R 3 both represent hydrogen and R 2 represents hydrogen or methyl; or wherein q represents zero or 1 , R-i and R 3 together form the -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 - groups and R 2 represents hydrogen.
  • Suitable hardener components are, for example, amine and anhydride hardeners such as polyamines, e.g. ethylenediamine, diethylenetriamine, triethylenetriamine, hexamethylenediamine, methanediamine, N-aminoethyl piperazine, diaminodi- phenylmethane [DDM], alkyl-substituted derivatives of DDM, isophoronediamine [IPD], diaminodiphenylsulphone [DDS], 4,4'-methylenedianiline [MDA], or m-phenylenediamine [MPDA]), polyamides, alkyl/alkenyl imidazoles, dicyandiamide [DICY], 1 ,6-hexamethylene-bis-cyanoguanidine, or acid anhydrides, e.g.
  • polyamines e.g. ethylenediamine, diethylenetriamine, triethylenetriamine, hexamethylenediamine, methanedia
  • dode- cenylsuccinic acid anhydride dode- cenylsuccinic acid anhydride, hexahydrophthalic acid anhydride, tetrahydrophthalic acid anhydride, phthalic acid anhydride, pyromellitic acid anhydride, and derivatives thereof.
  • thermoplastic polymers include poly- olefin homo- and copolymers, copolymers of olefins vinyl monomers, styrenic ho- mopolymers and copolymers thereof.
  • the melamine and guanidine salts (I) and (II) are ground to a fine powder with an average particle size below 100 ⁇ prior to their application in polymer substrates as it is observed that the flame retardant properties of the inventive compositions are improved by small particle sizes.
  • the instant invention further pertains to a composition, which comprises, in addition to the components a), b) and c), as defined above, as optional components, additional flame retardants and further additives selected from the group consisting of so-called anti-dripping agents and polymer stabilizers.
  • phosphorus containing flame retardants are for example:
  • Tetraphenyl resorcinol diphosphate (Fyrolflex ® RDP, Akzo Nobel), resorcinol diphosphate oligomer (RDP), triphenyl phosphate, tris(2,4-di-tert-butylphenyl)phosphate, ethylenediamine diphosphate (EDAP), ammonium polyphosphate, diethyl-N,N-bis(2- hydroxyethyl)-aminomethyl phosphonate, hydroxyalkyl esters of phosphorus acids, salts of [RX1 ]hypophosphoric acid (H 3 P0 2 ), particularly the Ca 2+ , Zn 2+ , or Al 3+ salts, tetrakis(hydroxymethyl)phosphonium sulphide, triphenylphosphine, derivatives of 9,10- dihydro-9-oxa-10-phosphorylphenanthrene-10-oxide (DOPO), and phosphazene flame- retardants.
  • Nitrogen containing flame retardants are, for example, isocyanurate flame retardants, such as polyisocyanurate, esters of isocyanuric acid or isocyanurates.
  • isocyanurate flame retardants such as polyisocyanurate, esters of isocyanuric acid or isocyanurates.
  • Representative examples are hydroxyalkyl isocyanurates, such as tris-(2-hydroxyethyl)isocyanurate, tris(hydroxymethyl)isocyanurate, tris(3-hydroxy-n-proyl)isocyanurate or triglycidyl iso- cyanurate.
  • Nitrogen containing flame-retardants include further melamine-based flame-retardants.
  • Representative examples are: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and di- melamine pyrophosphate.
  • benzoguanamine tris(hydroxyethyl) isocyanurate, allantoin, gly- coluril, melamine cyanurate, melamine phosphate, dimelamine phosphate, urea cyanurate, ammonium polyphosphate, a condensation product of melamine from the series melem, melam, melon and/or a higher condensed compound or a reaction prod- uct of melamine with phosphoric acid or a mixture thereof.
  • organohalogen flame retardants are, for example:
  • dibromo-norbornanedicarboximide (Saytex ® BN-451 ), bis-(hexachlorocycloentadeno) cyclooctane, PTFE, tris-(2,3-dibromopropyl)-isocyanurate, and ethylene-bis-tetrabro- mophthalimide.
  • organohalogen flame retardants mentioned above are routinely combined with an inorganic oxide synergist. Most common for this use are zinc or antimony oxides, e.g. Sb 2 0 3 or Sb 2 0 5 . Boron compounds are suitable, too.
  • Representative inorganic flame retardants include, for example, aluminum trihydroxide (ATH), boehmite (AIOOH), magnesium dihydroxide (MDH), zinc borates, CaC0 3 , (organically modified) layered silicates, (organically modified) layered double hydroxides, and mixtures thereof.
  • the above-mentioned additional flame retardant classes are advantageously contained in the composition of the invention in an amount from about 0.5% to about 60.0% by weight of the organic polymer substrate; for instance about 1 .0% to about 40.0%; for example about 5.0% to about 35.0% by weight of the polymer or based on the total weight of the composition.
  • the invention relates to a composition which additionally comprises as additional component so-called anti-dripping agents.
  • anti-dripping agents reduce the melt flow of the thermoplastic polymer and inhibit the formation of drops at high temperatures.
  • Suitable additives that inhibit the formation of drops at high temperatures include glass fibers, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibers, glass spheres and the like.
  • Stabilizers are preferably halogen-free and selected from the group consisting of ni- troxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methide stabilizers and monoacrylate esters of 2,2'-alkylidenebisphenol stabilizers.
  • composition according to the invention may additionally contain one or more conventional additives, for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-hydroxy-benzophenone, 2-(2'-hydroxyphenyl)- benzotriazole and/or 2-(2-hydroxyphenyl)-1 ,3,5-triazine groups.
  • additives for example selected from pigments, dyes, plasticizers, antioxidants, thixotropic agents, levelling assistants, basic co-stabilizers, metal passivators, metal oxides, organophosphorus compounds, further light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, UV absorbers of the 2-hydroxy-benzophenone, 2-(2'
  • Preferred additional additives for the compositions as defined above are processing stabilizers, such as the above-mentioned phosphites and phenolic antioxidants, and light stabilizers, such as benzotriazoles.
  • Preferred specific antioxidants include octade- cyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), pentaerythritol- tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (IRGANOX 1010), tris(3,5-di- tert-butyl-4-hydroxyphenyl)isocyanurate (IRGANOX 31 14), 1 ,3,5-trimethyl-2,4,6- tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene (IRGANOX 1330), triethyleneglycol- bis[3-(3- tert-
  • Specific processing stabilizers include tris(2,4-di-tert-butylphenyl)phosphite (IR- GAFOS 168), 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro- [5.5]undecane (IRGAFOS 126), 2,2',2"-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1 ,1 '- biphenyl-2,2'-diyl)]phosphite (IRGAFOS 12), and tetrakis(2,4-di-tert-butylphenyl)[1 ,1 - biphenyl]-4,4'-diylbisphosphonite (IRGAFOS P-EPQ).
  • Specific light stabilizers include 2-(2H-benzotriazole-2-yl)-4,6-bis(1 -methyl-1 -phenylethyl)phenol (TINUVIN 234), 2-(5- chloro(2H)-benzotriazole-2-yl)-4-(methyl)-6-(tert-butyl)phenol (TINUVIN 326), 2-(2H- benzotriazole-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol (TINUVIN 329), 2-(2H-benzo- triazole-2-yl)-4-(tert-butyl)-6-(sec-butyl)phenol (TINUVIN 350), 2,2'-methylenebis(6-(2H- benzotriazol-2-yl)-4-(1 ,1 ,3,3-tetramethylbutyl)phenol) (TINUVIN 360), and 2-(4,6-diphe- nyl-1 ,3,5-triazin-2-
  • the additives mentioned above are preferably contained in an amount of 0.01 to
  • the incorporation of the components defined above into the polymer component is carried out by known methods such as dry blending in the form of a powder, or wet mixing in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil.
  • the additive components a) and b) and optional further additives may be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or additive mixture to the polymer material, with or without subsequent evaporation of the solvent or the suspension/dispersion agent. They may be added di- rectly into the processing apparatus (e.g. extruders, internal mixers, etc.), e.g. as a dry mixture or powder, or as a solution or dispersion or suspension or melt.
  • the addition of the additive components to the polymer substrate can be carried out in customary mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.
  • the process is preferably carried out in an extruder by introducing the additive during processing.
  • Particularly preferred processing machines are single-screw extruders, contra-rotating and co-rotating twin-screw extruders, planetary-gear extruders, ring extruders or co- kneaders.
  • Processing machines provided with at least one gas removal compartment can be used to which a vacuum can be applied.
  • the screw length is 1 - 60 screw diameters, preferably 35-48 screw diameters.
  • the rotational speed of the screw is preferably 10 - 600 rotations per minute (rpm), preferably 25 - 300 rpm.
  • the maximum throughput is dependent on the screw diameter, the rotational speed and the driving force.
  • the process of the present invention can also be carried out at a level lower than maximum throughput by varying the parameters mentioned or employing weighing machines delivering dosage amounts.
  • the additive components a) and optional further additives can also be sprayed onto the polymer substrate b).
  • the additive mixture dilutes other additives, for example the conventional additives indicated above, or their melts so that they can be sprayed also together with these additives onto the polymer substrate.
  • Addition by spraying during the deactivation of the polymerisation catalysts is particularly advantageous; in this case, the steam evolved may be used for deactivation of the catalyst.
  • spheri- cally polymerised polyolefins it may, for example, be advantageous to apply the additives of the invention, optionally together with other additives, by spraying.
  • the additive components a) and b) optional further additives can also be added to the polymer in the form of a master batch ("concentrate") which contains the components in a concentration of, for example, about 1.0% to about 40.0% and preferably 2.0% to about 20.0% by weight incorporated in a polymer.
  • concentration a master batch
  • the polymer is not necessarily of identical structure than the polymer where the additives are added finally.
  • the polymer can be used in the form of powder, granules, solutions, and suspensions or in the form of lattices.
  • Incorporation can take place prior to or during the shaping operation.
  • the materials containing the additives of the invention described herein preferably are used for the production of molded articles, for example roto-molded articles, injection molded articles, profiles and the like, and especially a fibre, spun melt non-woven, film or foam.
  • the components a) and b) are admixed to the polymer substrate c) in concentrations of 0.1 - 45.0 wt.%, preferably 0.1 - 30.0 wt.% for component a) and 0.05 - 5.0 wt.%, pref- erably 0.1 - 2.0 wt.% for component b).
  • the preferred ratio of components a) : b) is in the range 50 : 1 - 1 : 5, preferably 20 : 1 - 1 : 2.
  • a particularly preferred embodiment of the invention relates to a composition, particularly a flame retardant composition, which comprises
  • R 1 and R 2 represents hydrogen or CrC 8 alkyl; or both R 1 and R 2 represent CrC 8 alkyl; and
  • R 3 represents CrCi 0 alkylene, C 2 -Ci 0 alkylene interrupted by phenylene, phenylene, (Ci-C 4 alkyl) 1-3 phenylene, or phenyl-Ci-C 4 alkylene; At least one tetraalkylpiperidine derivative III c or III d selected from the group consisting of
  • the oligomeric compound which is the condensation product of 4,4'-hexa- methylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1 - cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end- capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine,
  • n is from 1 to 15.
  • thermoplastic polymer selected from the group consisting of polyolefin ho- mopolymers and copolymers of olefins with each other or with vinyl monomers.
  • Moplen® HF500 N Commercial grade polypropylene (Basell, Germany);
  • Tinuvin® NOR 371 (NOR 1 ): Commercial product (Ciba Inc., Switzerland);
  • Exolit OP® 1240 Diethylphosphinic acid aluminium salt (Clariant, Switzerland).
  • a basic-level stabilization composition (0.05% Ca-stearate + 0.5% IRGANOX® B225; IRGANOX® B225 is a 1 :1 mixture of IRGAFOS® 168 and IRGANOX® 1010) and the additives listed in Table 1 .
  • test samples are investigated for their flame retardant behaviour in accordance with UL94-V standards after conditioning for 48 h at 23°C and 50% relative humidity.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne des compositions polymères ignifuges qui comprennent des mélanges de sels d'acides phosphiniques et de 2,2,6,6-tétra-alkylpipéridines. Ces mélanges sont particulièrement utiles dans l'élaboration de compositions ignifuges à base polymères thermoplastiques.
PCT/EP2011/054387 2010-03-25 2011-03-23 Compositions ignifuges à base de sels d'acides phosphiniques et de dérivés de nitroxyle Ceased WO2011117266A1 (fr)

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KR1020127027987A KR20120135428A (ko) 2010-03-25 2011-03-23 포스핀산 염 및 니트록실 유도체의 난연성 조성물
JP2013500478A JP5615425B2 (ja) 2010-03-25 2011-03-23 ホスフィン酸塩およびニトロキシル誘導体の難燃性組成物
EP11709427A EP2550321A1 (fr) 2010-03-25 2011-03-23 Compositions ignifuges à base de sels d'acides phosphiniques et de dérivés de nitroxyle
CN2011800153548A CN102834445A (zh) 2010-03-25 2011-03-23 次膦酸盐和硝酰基衍生物的阻燃剂组合物
KR20157001653A KR20150024901A (ko) 2010-03-25 2011-03-23 포스핀산 염 및 니트록실 유도체의 난연성 조성물
BR112012023783A BR112012023783A2 (pt) 2010-03-25 2011-03-23 composição, mistura, e, processo para conferir retardâncias de chama a um substrato de polímero
RU2012145171/04A RU2012145171A (ru) 2010-03-25 2011-03-23 Огнезащитные композиции солей фосфиновых кислот и нитроксильных производных

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102838842A (zh) * 2012-09-14 2012-12-26 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
CN102850722A (zh) * 2012-09-07 2013-01-02 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
DE102013005307A1 (de) 2013-03-25 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von organischen Oxyimiden als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffzusammensetzung und hieraus hergestelltem Formteil
DE102013012487A1 (de) 2013-07-26 2015-01-29 Clariant International Ltd. Zusammensetzung aus einem thermoplastischen Polymer und einer synergistischen Mischung aus bestimmten Aminoethern und feinteiligen Phosphinaten
WO2015189034A1 (fr) 2014-06-12 2015-12-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Utilisation de dérivés de n-hydroxybenzotriazole et/ou de dérivés de n-hydroxy-indazoles comme agent ignifuge pour matières plastiques et également matière plastique de moulage ignifugée
US10214631B2 (en) 2012-11-19 2019-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polymer composition with improved long-term stability, moulded parts produced herefrom and also purposes of use
WO2019092163A1 (fr) 2017-11-13 2019-05-16 Clariant Plastics & Coatings Ltd Nouvelles compositions ignifuges pour polyoléfines
US10370537B2 (en) 2014-05-28 2019-08-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of oxyimide-comprising copolymers or polymers as flame retardants, stabilisers, rheology modifiers for plastic materials, initiators for polymerisation- and grafting processes, crosslinking- or coupling agents and also plastic moulding compounds comprising such copolymers or polymers
WO2020115522A1 (fr) 2018-12-03 2020-06-11 Italmatch Chemicals S.P.A. Compositions de polyoléfines à mouler ignifuges sans halogène comprenant un sel métallique inorganique d'acide hypophosphoreux
EP4365225A1 (fr) 2022-11-04 2024-05-08 Clariant International Ltd Composition ignifuge, composition polymère la comprenant et son utilisation
WO2025190075A1 (fr) * 2024-03-15 2025-09-18 上海金发科技发展有限公司 Retardateur de flamme exempt d'halogène à faible acidité et son procédé de préparation, ainsi que matériau composite polyamide ignifuge et son application

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KR102830470B1 (ko) * 2020-02-21 2025-07-04 피에스 저팬 가부시끼가이샤 스티렌계 수지 조성물, 난연성 스티렌계 수지 조성물 및 성형체, 그리고 패치 안테나
JP7552114B2 (ja) * 2020-07-15 2024-09-18 株式会社レゾナック 樹脂組成物及び導体基板
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JP2024149247A (ja) * 2023-04-07 2024-10-18 出光ファインコンポジット株式会社 樹脂組成物

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030331A (en) 1957-08-22 1962-04-17 Gen Electric Process for preparing copolyesters comprising reacting a carbonyl halide with a dicarboxylic acid and a dihydroxy compound in the presence of a tertiary amine
US3169121A (en) 1957-08-22 1965-02-09 Gen Electric Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids
US4130458A (en) 1975-06-20 1978-12-19 Masonite Corporation Product containing alumina trihydrate and a source of B2 O3 and method
US4263201A (en) 1978-12-07 1981-04-21 General Electric Company Flame retardant polycarbonate composition
US4286083A (en) 1976-12-29 1981-08-25 General Electric Company Method of preparing polyester carbonates
US4552704A (en) 1983-12-27 1985-11-12 General Electric Company Process for the production of aromatic carbonates
US5004770A (en) 1988-10-19 1991-04-02 Ciba-Geigy Corporation Polymeric substrates stabilized with N-substituted hindered amines
US5096950A (en) 1988-10-19 1992-03-17 Ciba-Geigy Corporation Polyolefin compositions stabilized with NOR-substituted hindered amines
US5112890A (en) 1987-09-21 1992-05-12 Ciba-Geigy Corporation Stabilization of acid catalyzed thermoset resins
US5124378A (en) 1987-09-21 1992-06-23 Ciba-Geigy Corporation Stabilization of ambient cured coatings
US5145893A (en) 1989-03-21 1992-09-08 Ciba-Geigy Corporation Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers
US5204473A (en) 1987-09-21 1993-04-20 Ciba-Geigy Corporation O-substituted N-hydroxy hindered amine stabilizers
US5210268A (en) 1989-12-28 1993-05-11 Asahi Kasei Kogyo Kabushiki Kaisha Process for continuously producing an aromatic carbonate
US5216156A (en) 1992-05-05 1993-06-01 Ciba-Geigy Corporation Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-triazine derivatives
US5606007A (en) 1989-12-28 1997-02-25 General Electric Company Processes for preparing aromatic polycarbonates
US5844026A (en) 1997-06-30 1998-12-01 Ciba Specialty Chemicals Corporation N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith
EP0896023A1 (fr) * 1997-08-08 1999-02-10 Clariant GmbH Combination synergistique d'agents ignifugeants pour les polymères
US6117995A (en) 1998-02-25 2000-09-12 Ciba Specialty Chemicals Corporation Preparation of sterically hindered amine ethers
US6271377B1 (en) 1999-02-25 2001-08-07 Ciba Specialty Chemicals Corporation Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith
WO2001090113A1 (fr) 2000-05-19 2001-11-29 Ciba Specialty Chemicals Holding Inc. Esters d'hydroxylamine initiateurs de polymerisation
US6660787B2 (en) 2001-07-18 2003-12-09 General Electric Company Transparent, fire-resistant polycarbonate compositions
US6727302B2 (en) 2001-04-03 2004-04-27 General Electric Company Transparent, fire-resistant polycarbonate
US6730720B2 (en) 2000-12-27 2004-05-04 General Electric Company Method for reducing haze in a fire resistant polycarbonate composition
EP1454948A2 (fr) * 2003-03-03 2004-09-08 Clariant GmbH Combinaison d'agent ignifugeant et stabilisant pour polymères thermoplastiques

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3023490B2 (ja) * 1991-05-29 2000-03-21 住化プラステック株式会社 酸化防止性樹脂組成物
DE69826477T2 (de) * 1997-06-30 2005-11-17 Ciba Speciality Chemicals Holding Inc. Flammhemmende zusammensetzungen
AU2001233764A1 (en) * 2000-02-22 2001-09-03 Ciba Specialty Chemicals Holding Inc. Stabilizer mixtures for polyolefins
DE10317487A1 (de) * 2003-04-16 2004-01-22 Ticona Gmbh Flammschutzmittel-Kombination und flammgeschützte thermoplastische Formmassen
ATE346883T1 (de) * 2003-07-18 2006-12-15 Ciba Sc Holding Ag Flammwidrige polymilchsäure
JP2008038149A (ja) * 2005-11-10 2008-02-21 Asahi Kasei Chemicals Corp 難燃性に優れた樹脂組成物
WO2007088114A1 (fr) * 2006-02-01 2007-08-09 Ciba Holding Inc. Préparation stabilisante pour polymères
WO2009031284A1 (fr) * 2007-09-03 2009-03-12 Unitika Ltd. Composition de résine et corps moulé à l'aide de celle-ci
EP2225318B1 (fr) * 2007-12-21 2011-08-03 Basf Se Compositions ignifugeantes comprenant des amines à empêchement stérique
JP5129018B2 (ja) * 2008-05-15 2013-01-23 旭化成ケミカルズ株式会社 難燃性樹脂組成物

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3030331A (en) 1957-08-22 1962-04-17 Gen Electric Process for preparing copolyesters comprising reacting a carbonyl halide with a dicarboxylic acid and a dihydroxy compound in the presence of a tertiary amine
US3169121A (en) 1957-08-22 1965-02-09 Gen Electric Carbonate-carboxylate copolyesters of dihydric phenols and difunctional carboxylic acids
US4130458A (en) 1975-06-20 1978-12-19 Masonite Corporation Product containing alumina trihydrate and a source of B2 O3 and method
US4286083A (en) 1976-12-29 1981-08-25 General Electric Company Method of preparing polyester carbonates
US4263201A (en) 1978-12-07 1981-04-21 General Electric Company Flame retardant polycarbonate composition
US4552704A (en) 1983-12-27 1985-11-12 General Electric Company Process for the production of aromatic carbonates
US5112890A (en) 1987-09-21 1992-05-12 Ciba-Geigy Corporation Stabilization of acid catalyzed thermoset resins
US5124378A (en) 1987-09-21 1992-06-23 Ciba-Geigy Corporation Stabilization of ambient cured coatings
US5204473A (en) 1987-09-21 1993-04-20 Ciba-Geigy Corporation O-substituted N-hydroxy hindered amine stabilizers
US5004770A (en) 1988-10-19 1991-04-02 Ciba-Geigy Corporation Polymeric substrates stabilized with N-substituted hindered amines
US5096950A (en) 1988-10-19 1992-03-17 Ciba-Geigy Corporation Polyolefin compositions stabilized with NOR-substituted hindered amines
US5145893A (en) 1989-03-21 1992-09-08 Ciba-Geigy Corporation Non-migrating 1-hydrocarbyloxy hindered amine derivatives as polymer stabilizers
US5210268A (en) 1989-12-28 1993-05-11 Asahi Kasei Kogyo Kabushiki Kaisha Process for continuously producing an aromatic carbonate
US5606007A (en) 1989-12-28 1997-02-25 General Electric Company Processes for preparing aromatic polycarbonates
US5216156A (en) 1992-05-05 1993-06-01 Ciba-Geigy Corporation Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidine 1,3,5-triazine derivatives
US5300544A (en) 1992-05-05 1994-04-05 Ciba-Geigy Corporation Non-migrating 1-hydrocarbyloxy-2,2,6,6-tetramethylpiperdine 1,3,5-triazine derivatives as polymer stabilizers
US5844026A (en) 1997-06-30 1998-12-01 Ciba Specialty Chemicals Corporation N,N',N''-tris{2,4-bis Hydrocarbyloxy-2,2,6,6-tetra-methylpiperidin-4-yl)alkylamino!-s-triazin-6-yl}-3,3'-ethylenediiminodipropylamines, their isomers and bridged derivatives and polymer compositions stabilized therewith
EP0896023A1 (fr) * 1997-08-08 1999-02-10 Clariant GmbH Combination synergistique d'agents ignifugeants pour les polymères
US6117995A (en) 1998-02-25 2000-09-12 Ciba Specialty Chemicals Corporation Preparation of sterically hindered amine ethers
US6271377B1 (en) 1999-02-25 2001-08-07 Ciba Specialty Chemicals Corporation Hydroxy-substituted N-alkoxy hindered amines and compositions stabilized therewith
WO2001090113A1 (fr) 2000-05-19 2001-11-29 Ciba Specialty Chemicals Holding Inc. Esters d'hydroxylamine initiateurs de polymerisation
US6730720B2 (en) 2000-12-27 2004-05-04 General Electric Company Method for reducing haze in a fire resistant polycarbonate composition
US6727302B2 (en) 2001-04-03 2004-04-27 General Electric Company Transparent, fire-resistant polycarbonate
US6660787B2 (en) 2001-07-18 2003-12-09 General Electric Company Transparent, fire-resistant polycarbonate compositions
EP1454948A2 (fr) * 2003-03-03 2004-09-08 Clariant GmbH Combinaison d'agent ignifugeant et stabilisant pour polymères thermoplastiques

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Extrusionsanlagen", vol. 2, 1986
"Flammability of Plastic Materials for Parts in Devices and Appliances", 29 October 1996
"Grundlagen", vol. 1, 1989, article "Handbuch der Kunststoffextrusion", pages: 3 - 7

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* Cited by examiner, † Cited by third party
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CN102850722A (zh) * 2012-09-07 2013-01-02 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
CN102838842A (zh) * 2012-09-14 2012-12-26 广东生益科技股份有限公司 环氧树脂组合物以及使用其制作的半固化片与覆铜箔层压板
US10214631B2 (en) 2012-11-19 2019-02-26 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polymer composition with improved long-term stability, moulded parts produced herefrom and also purposes of use
DE102013005307A1 (de) 2013-03-25 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von organischen Oxyimiden als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffzusammensetzung und hieraus hergestelltem Formteil
US10913743B2 (en) 2013-03-25 2021-02-09 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of organic oxyimides as flame retardant for plastic materials and also flame-retardant plastic material composition and moulded parts produced therefrom
DE102013012487A1 (de) 2013-07-26 2015-01-29 Clariant International Ltd. Zusammensetzung aus einem thermoplastischen Polymer und einer synergistischen Mischung aus bestimmten Aminoethern und feinteiligen Phosphinaten
US9732202B2 (en) 2013-07-26 2017-08-15 Clariant International Ltd. Composition comprising a thermoplastic polymer and a synergistic mixture of determined amino ethers and finely particled phosphinates
US10370537B2 (en) 2014-05-28 2019-08-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of oxyimide-comprising copolymers or polymers as flame retardants, stabilisers, rheology modifiers for plastic materials, initiators for polymerisation- and grafting processes, crosslinking- or coupling agents and also plastic moulding compounds comprising such copolymers or polymers
WO2015189034A1 (fr) 2014-06-12 2015-12-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Utilisation de dérivés de n-hydroxybenzotriazole et/ou de dérivés de n-hydroxy-indazoles comme agent ignifuge pour matières plastiques et également matière plastique de moulage ignifugée
US10323136B2 (en) 2014-06-12 2019-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Use of hydroxybenzotriazole derivatives and/or hydroxy indazole derivatives as flame retardants for plastics and flameproof plastic moulded bodies
DE102014211276A1 (de) 2014-06-12 2015-12-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von Hydroxybenzotriazol-Derivaten und/oder Hydroxy-Indazol-Derivaten als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffformmasse
WO2019092163A1 (fr) 2017-11-13 2019-05-16 Clariant Plastics & Coatings Ltd Nouvelles compositions ignifuges pour polyoléfines
WO2020115522A1 (fr) 2018-12-03 2020-06-11 Italmatch Chemicals S.P.A. Compositions de polyoléfines à mouler ignifuges sans halogène comprenant un sel métallique inorganique d'acide hypophosphoreux
US20220017725A1 (en) * 2018-12-03 2022-01-20 Italmatch Chemicals S.P.A. Polyolefins halogen-free flame retardant moulding compositions comprising an inorganic hypophosphorous acid metal salt
US11807735B2 (en) 2018-12-03 2023-11-07 Italmatch Chemicals S.P.A. Polyolefins halogen-free flame retardant moulding compositions comprising an inorganic hypophosphorous acid metal salt
EP4365225A1 (fr) 2022-11-04 2024-05-08 Clariant International Ltd Composition ignifuge, composition polymère la comprenant et son utilisation
WO2024094455A1 (fr) 2022-11-04 2024-05-10 Clariant International Ltd Composition ignifuge, composition polymère la comprenant et son utilisation
WO2025190075A1 (fr) * 2024-03-15 2025-09-18 上海金发科技发展有限公司 Retardateur de flamme exempt d'halogène à faible acidité et son procédé de préparation, ainsi que matériau composite polyamide ignifuge et son application

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JP5615425B2 (ja) 2014-10-29
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KR20120135428A (ko) 2012-12-13
TW201202325A (en) 2012-01-16
KR20150024901A (ko) 2015-03-09
CN102834445A (zh) 2012-12-19
RU2012145171A (ru) 2014-04-27

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