WO2005121234A2 - Composition polymere ignifuge presentant une stabilite thermique accrue - Google Patents

Composition polymere ignifuge presentant une stabilite thermique accrue Download PDF

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Publication number
WO2005121234A2
WO2005121234A2 PCT/US2005/029791 US2005029791W WO2005121234A2 WO 2005121234 A2 WO2005121234 A2 WO 2005121234A2 US 2005029791 W US2005029791 W US 2005029791W WO 2005121234 A2 WO2005121234 A2 WO 2005121234A2
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WIPO (PCT)
Prior art keywords
component
tert
hydroxide
polymer composition
butyl
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PCT/US2005/029791
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English (en)
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WO2005121234A3 (fr
Inventor
Glenn P. Desio
Linda M. Norfolk
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Solvay Advanced Polymers, L.L.C.
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Application filed by Solvay Advanced Polymers, L.L.C. filed Critical Solvay Advanced Polymers, L.L.C.
Priority to PCT/US2005/029791 priority Critical patent/WO2005121234A2/fr
Publication of WO2005121234A2 publication Critical patent/WO2005121234A2/fr
Publication of WO2005121234A3 publication Critical patent/WO2005121234A3/fr
Priority to IT001614A priority patent/ITMI20061614A1/it
Priority to BE2006/0431A priority patent/BE1020167A3/fr
Priority to FR0607329A priority patent/FR2900409B1/fr
Priority to CH01327/06A priority patent/CH696700A5/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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

Definitions

  • the invention relates to a thermally stable flame retarded polymer composition
  • a semi-aromatic polyamide derived from at least one aromatic diamine comprising a semi-aromatic polyamide derived from at least one aromatic diamine.
  • the invention also relates to a shaped article made of said polymer composition.
  • Semi-aromatic polyamides like those derived from phthalic acids and aliphatic diamines, i.e. polyphthalamides, or those derived from aromatic diamines and aliphatic diacids
  • compositions based on these semi- aromatic polyamides notably those derived from aromatic diamines and aliphatic diacids, be flame retarded, so as to meet UL 94 V-0 standard for high degree of flame retardance.
  • a method generally used to impart flame retardance to polymers involves incorporating halogenated flame retardant agents.
  • halogenated flame retardants tend to thermally decompose at the molding temperature. The halogenated degradation products corrode the surfaces of the compounding extruder and impart poor surface appearance to the molded articles.
  • prior art halogenated flame retarded compositions based on polyamide derived from aromatic diamines are rather unstable during melt processing, that resulting in degradation and/or decomposition problems like discoloration, out gassing, blooming at the surface of the molded article and molecular weight degradation of the polymer matrix.
  • flame retarded compositions in particular those based on polyamides derived from adipic acid and m- xylylenediamine (i.e. MXD6 polyamides), would not only comply with UL 94 V-0 standard, but also have excellent thermal stability and mold ability.
  • thermoplastic polymers like for example polyolefins, polystyrene, halogenated polymers, polyacetals, polycarbonates, polysulfones, polyetherketones, polyamides, polyesters), preferably engineering plastics and especially polyesters.
  • WO0066658 describes the utilization of carbodiimides, isocyanates and isocyanurates for the purpose of stabilizing polymer molding compositions containing phosphorous-based flame retardants.
  • halogen free flame retarded polyamide compositions wherein the polyamide is an aliphatic polyamide or a polyphthalamide and the flame retardant is a metal phosphinate, alone or in combination with other synergists, are relatively well described in the prior art (US 2005/014874), the same cannot be said for those halogen free flame retarded polyamide compositions wherein the polyamide is a semi-aromatic polyamide derived from at least one aromatic diamine, like for example MXD6 polyamides.
  • thermoplastic polymers wherein the thermoplastic polymer can be MXD6 polyamides or polyamides including an aromatic diamine like xylylendiamine and wherein the flame retardant is a metal phosphinate in combination, optionally or not, with a nitrogen synergist.
  • the flame retardant is a metal phosphinate in combination, optionally or not, with a nitrogen synergist.
  • flame retardant and stabilizer combined agents have been described by US 2004/ 0227130 for a wide variety of different thermoplastic polymers, but these agents are reported to be effective especially for polyesters and aliphatic polyamides like nylon-6 and nylon 6-6. From the foregoing discussion it results that further research is needed in this area, especially in order to understand which is the flame retardant behavior, the thermal stability and the mold ability of halogen free flame retarded polyamide compositions based on aromatic polyamides derived from at least one aromatic diamine.
  • a flame retarded polyamide composition based on a semi-aromatic polyamide comprising recurring units derived from a dicarboxylic acid component including at least one aliphatic dicarboxylic acid and a diamine component including at least one - aromatic -diamine, wherein said composition, besides complying withUL 94 V-0 standard for high degree of flame retardance, would also have excellent thermal stability so as to be molded without encountering any of the degradation and/or discoloration problems previously mentioned.
  • the invention therefore provides a flame retarded and thermally stabilized polymer composition
  • a flame retardant and stabilizer combined agent comprising ⁇ as component (A), a flame retardant selected from the group consisting of a phosphinic salt of the formula (I), a diphosphinic salt of the formula (II), polymers of the formula (I), polymers of the formula (LI) and mixtures thereof,
  • R 1 , R 2 are identical or different and are Cl-C-alkyl, linear or branched, or aryl;
  • R 3 is Cl-ClO-alkylene, linear or branched, C6- ClO-arylene, alkylarylene or arylalkylene;
  • M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, or a protonated nitrogen base;
  • m is 1 to 4;
  • n is 1 to 4;
  • x is 1 to 4, - as component (B), a flame retardant synergist selected from the group of nitrogen-containing synergists and phosphorus/nitrogen-containing synergists
  • a thermal stabilizer selected from the group of basic or amphoteric oxide, hydroxide, carbonate, silicate, borate, stannate, mixed oxide/hydroxide, xide/hydroxide/carbonate, hydroxide/silicate, hydroxide/borate, or a mixture thereof
  • R-[P(OR 1 ) 2 ] m (I) characterized in that R is a mono- or polyvalent aliphatic, aromatic, or heteroaromatic organic radical and Ri is a compound of the structure (II) ry. i ⁇ )
  • A is a direct bond, O, S, Cl-18-alkylene (linear or branched), or Cl-18-alkylidene (linear or branched);
  • R 2 independently of one another, are Cl-2-alkyl (linear or branched), Cl-12-alkoxy, or C5-12- cycloalkyl; and n is from 0 to 5, and m is from 1 to 4, ⁇ optionally as component (E), an ester or salt of montan wax acid, ⁇ optionally as component (F), aN,N'-bispiperidinyl-l,3-benzenedicarboxamide and/or N,N , -bis(2,2,6,6-tetramethyl-4-piperidinyl)-l,3-benzenedicarboxamide, said polymer composition being characterized in that the thermoplastic polymer (i) is a semi-aromatic polyamide comprising recurring units derived from a dicarboxylic acid component including at least one aliphatic dicar
  • the inventive aromatic polyamide composition provides reduced discoloration during processing in the melt, reduced degradation together with full retention of flame retardancy.
  • M is preferably calcium, aluminum or zinc.
  • the protonated nitrogen bases are preferably the protonated bases of ammonia, melamine, triethanolamine, in particular NH 4 + .
  • R 1 and R 2 are preferably Cl-C6-alkyl, linear or branched, and/or phenyl.
  • R and R identical or different, are particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl.
  • R 3 is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert- butylene, n-pentylene, n-octylene, or n-dodecylene. Another preferred meaning of R 3 is phenylene or naphthylene.
  • Suitable phosphinates have been described in US 6,365,071 expressly incorporated herein by way of reference. Particularly preferred phosphinates are aluminum phosphinates, calcium phosphinates, and zinc phosphinates.
  • Synergistic combinations of the specified phosphinates with nitrogen- containing compounds which have more effective action as flame retardants than the phosphinates alone in very many polymers are also in accordance with the invention.
  • the flame-retardant action of the phosphinates may be improved via combination with other flame retardants, preferably nitrogen-containing synergists, or phosphorus/nitrogen flame retardants.
  • the nitrogen-containing synergist of component (B) is of the formulae (III) to (VIII), or a mixture thereof
  • R 5 to R 7 are hydrogen, Cl-C8-alkyl, C5-C16-cycloalkyl or - alkylcycloalkyl, optionally substituted with a hydroxy or a Cl-C4-hydroxyalkyl function, C2-C8-alkenyl, Cl-C8-alkoxy, -acyl, -acyloxy, C6-C12-aryl or - arylalkyl, -OR 8 , or -N(R 8 )R 9 , or a N-alicyclic or N-aromatic system;
  • R 8 is hydrogen, Cl-C8-alkyl, C5-C16-cycloalkyl or -alkylcycloalkyl, optionally substituted with a hydroxy or a Cl-C4-hydroxyalkyl function, C2-C8-alkenyl, Cl-C8-alkoxy, -acyl, -acyloxy, or C6-C12-aryl or -arylalky
  • the nitrogen-containing synergists preferably comprise benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, dicyandiamide, guanidine, carbodiimides.
  • the nitrogen-containing synergists preferably comprise condensation products of melamine.
  • condensation products of melamine are melem , melam, or melon, or compounds of this type with a higher condensation level, or else a mixture of the same, and, by way of example, may be prepared by the process described in US 5,985,960.
  • the phosphorus/mtrogen-containing synergists may comprise reaction products of melamine with phosphoric acid or with condensed phosphoric acids, or comprise reaction products of condensation products of melamine with phosphoric acid or. condensed phosphoric acids, or else comprise a mixture of the specified products.
  • the reaction products with phosphoric acid or with condensed phosphoric acids are compounds which arise via reaction of melamine or of the condensed melamine compounds, such as melam, melem, or melon etc., with phosphoric acid.
  • these are dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate, and mixed polysalts, e.g. those described in US 6,121,445 and US 6,136,973.
  • the phosphorus/nitrogen-containing synergist may also be ammonium hydrogenphosphate, ammonium dihydrogenphosphate, or ammonium polyphosphate.
  • the phosphorus/nitrogen-containing synergist of component (B) is at least one nitrogen containing phosphate selected from the group of melamine polyphosphate, ammonium hydrogenophosphate, ammonium dihydrogenophosphate, and ammonium polyphosphate.
  • Additives may be added to the phosphinates alone or in combination with phosphorus/nitrogen flame retardants, examples of these additives being: 1. Antioxidants
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylph- enol, 2- butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl- 4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4- methylphenol, 2- ⁇ -mefhylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl- 4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(l '- methylundec- -yl)phenol, 2,4-dimethyl-6-( -methylheptade
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert- butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl- 6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylpheno- 1.
  • 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, to (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, /3-tocopherol, ⁇ -tocopherol, ⁇ - tocopherol, and mixtures thereof (vitamin E).
  • thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4- methyrphenol), 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.
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-buty- 1-4- methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethyl ⁇ henol), 2,2'- methylenebis[4-methyl-6-(o;-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-bu- tyl-4- isobutylphenol), 2,2'-methylenebis[6-( ⁇ !-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ !-
  • O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'- dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercapto acetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, (4-tert-butyl-3- hydroxy-2,6-dimethylbenzyl) dithioterephthalate, (3 ,5-di-tert-butyl-4- hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4- hydroxybenzylmercaptoacetate.
  • Hydroxybenzylated malonates for example dioctadecyl 2,2-bis(3,5-di-tert- butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate, didodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl- 4-hydroxybenzyl)malonate, di-[4-(l,l,3,3-tetramethylbutyl)phenyl] 2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hydroxybenzyl compounds for example l,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-b ⁇ xtyl-4- hydroxybenzyl)phenol.
  • l.lOTriazine compounds for example 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl- 4-hydroxyanilino)- 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl- 4-hydroxyanilino)-l,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)-l,2,3-triazine, l,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl) isocyanurate, l,3,5-tris(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl) iso
  • Benzylphosphonates for example dimethyl 2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3- methylbenzylphosphonate, the Ca salt of the monoethyl ester of 3,5-di-tert- butyl-4-hydroxybenzylphosphonic acid.
  • esters of /3-(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)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha- 2,6,7-trioxabicyclo[2.2.2]octane.
  • 2-(2'-Hydroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hy- droxyphenyl)- benzotriazole, 2-(5'-tert-butyl-2 , -hydroxyphenyl)benzotriazol- e, 2-(2'- hydroxy-5'-(l, 1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'- hydroxyphenyl)benzotriazole,
  • Esters of substituted or unsubstituted benzoic acids for example 4-tert- butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, to (4-tert-butylbenzoyl)resorcinol, benzoyhesorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5- di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4- hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thiobis[4-(l, 1,3,3- tetramethylbutyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl- diethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of 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 undecyl ketoxime, nickel complexes of 1 -phenyl- 4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl- diethanolamine, nickel dibutyld
  • Sterically hindered amines for example to (2,2,6,6-tetramethylpiperidyl) sebacate, to (2,2,6,6-tetramethylpiperidyl- ) succinate, to (1,2,2,6,6- pentamethylpiperidinyl) sebacate, to (1,2,2,6,6-pentamethylpiperidyl) n- butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis(2,2,6,6-tetramethy- 1-4- piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-l,3,- 5- s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl) nitri
  • Oxalamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert- butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylamino- propyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p- methoxy-disubstituted and of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example, N,N'-diphenyloxalamide, N-salicylal-N'- salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-l,2,4- triazole, 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, (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, isodecyloxy pentaerythritol diphosphite, (2,4-d
  • Peroxide degraders e.g. esters of jS-thiodipropionic acid, for example the lauryl, stearyl, myristyl, or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerytliritol tetrakis(/3-dodecylmercapto)propionate.
  • Polyamide stabilizers e.g. copper salts in combination with iodides and/or phosphorus compounds; salts of divalent manganese.
  • Basic costabilizers e.g. melamme, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, the alkali metal and alkaline earth metal salts of higher fatty acids, examples being Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate, or tin pyrocatecholate.
  • Nucleating agents e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
  • Fillers and reinforcing agents e.g. calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides, and metal hydroxides, carbon black, graphite. 10.
  • Other additives e.g. plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • the thermal stabilizer corresponding to component (C) is for example: magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, magnesium hydroxide, hydrotalcite, hydrocalumite, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate, zinc stannate, and/or zinc hydroxide.
  • the thermal stabilizer is zinc borate, magnesium hydroxide, zinc hydroxide, dihydrotalcite, and/or boehmite. More preferably, the thermal stabilizer is zinc borate.
  • Zinc borate useful for the present invention is preferably anhydrous zinc borate with less than 0.2 wt. % of water (as described in US 5,204,400) and, more preferably, with no measurable water content like XPI-187 zinc borate from U.S. Borax.
  • Phosphonites of the structure are suitable as component D, where
  • R is a mono- or polyvalent aliphatic, aromatic, or heteroaromatic organic radical, and R : is a compound of the structure (II)
  • A is a direct bond, O, S, Cl-18-alkylene (linear or branched), or Cl-18- alkylidene (linear or branched), where R 2 independently of one another, are Cl-
  • R t a group of the structure (II) or (III), where R 2 , independently of one another, are Cl-8-alkyl (linear or branched), Cl-
  • A is a direct bond, O, Cl-8-alkylene (linear or branched), Cl-8-alkylidene (linear or branched), and n is from 0 to 3, and m is from 1 to 3.
  • Particularly preferred radicals are
  • R 2 independently of one another, are Cl-8-alkyl (linear or branched), Cl-8- alkoxy, cyclohexyl A is a direct bond, O, Cl-6-alkylidene (linear or branched), and n is from 1 to 3, and m is 1 or 2.
  • R ! is as defined above P(OR ⁇ ) 3 (TV).
  • n may be 0 or 1
  • these mixtures may also optionally comprise proportions of the compound (VII) or (VIII):
  • Esters or salts of long-chain aliphatic carboxylic acids are suitable as component (E).
  • the esters comprise reaction products of the specified carboxylic acids with familiar polyhydric alcohols, e.g. ethylene glycol, glycerol, trimethylolpropane, or pentaerythritol.
  • the alkali metal or alkaline earth metal salts, or aluminum salts and zinc salts of the specified carboxylic acids are in particular used.
  • Component (E) preferably comprises esters or salts of stearic acid, e.g. glycerol monostearate or calcium stearate.
  • Component (E) preferably comprises reaction products of montan wax acids with ethylene glycol.
  • the reaction products preferably comprise a mixture composed of the mono- and di- (ethylene glycol) esters of montan wax acid, montan wax acids, and ethylene glycol.
  • the reaction products particularly preferably comprise a mixture composed of the mono- and di(l,3-butanediol) esters of montan wax acid, montan wax acids, 1,3-butanediol, calcium montanate, and the calcium salt.
  • Carboxylic (ester) amides are suitable as component (F).
  • Component (F) preferably comprises a derivative of an aromatic di- or tricarboxylic (ester) amide.
  • the derivative preferably comprises N,N'-bispiperidmyl-l,3-benzene- dicarboxamide.
  • the derivative particularly preferably comprises N,N'-bis(2,2,6,6-tetra- methyl-4-piperdinyl)- 1 ,3 -benzenedicarboxamide.
  • the quantitative proportions of components (A), (B), and (C) in the flame retardant and stabilizer combined agent depend in essence on the intended application sector, and may vary within wide limits.
  • the flame retardant and stabilizer combined comprises from 25 to 99.9% by weight of component (A), from 0 to 75% by weight of component (B), and from 0.1 to 50% by weight of component (C), from 0 to 5% by weight of component (D), from 0 to 5% by weight of component (E), and from 0.1 to 5% by weight of component (F).
  • the flame retardant and stabilizer combined agent preferably comprises from 50 to 90% by weight of component (A), from 0 to 50%) by weight of component (B), from 1 to 20% by weight of component (C), from 0 to 5% by weight of component (D), from 0 to 5% by weight of component (E), and from 0.1 to 5% by weight of component (F).
  • the flame retardant and stabilizer combined agent particularly preferably comprises from 50 to 80%> by weight of component (A), from 20 to 50% by weight of component (B), and from 2 to 20% by weight of component (C), from 0 to 3% by weight of component (D), from 0 to 3% by weight of component (E), and from 0.1 to 4% by weight of component (F).
  • the inventive flame retardant and stabilizer combined may also comprise carbodiimides.
  • the aliphatic dicarboxylic acid used for the preparation of the semi- aromatic polyamide is advantageously chosen from the group of the linear aliphatic ⁇ , ⁇ -dicarboxylic acids and alicyclic dicarboxylic acids. It is possible to use a single acid or a mixture of acids.
  • the aliphatic dicarboxylic acid is preferably a linear aliphatic acid containing from 4 to 12 carbon atoms and, more preferably it is adipic acid.
  • the dicarboxylic acid component may further comprise dicarboxylic acids other than aliphatic dicarboxylic acids, for example aromatic dicarboxylic acids.
  • the aromatic diamine is advantageously meta-xylylenediamine, para- xylylenediamine or a mixture of these.
  • the aromatic diamine is m- xylylenediamine.
  • the diamine component may further comprise at least one diamine chosen from the group of linear aliphatic diamines, alicyclic diamines, aromatic diamines other than xylylenediamines.
  • the semi-aromatic polyamide may further comprise copolymerized recurring units derived from at least one - ⁇ aminocarboxylic acid and/or at least one lactam.
  • the semi-aromatic polyamide comprises recurring units derived from at least one linear aliphatic dicarboxylic acid containing from 4 to 12 carbon atoms and at least one xylylenediamine. More preferably, the semi-aromatic polyamide comprises recurring units derived from adipic acid and m-xylylenediamine. Still more preferably, the semi-aromatic polyamide consists of recurring units derived from adipic acid and m-xylylenediamine.
  • the flame retarded and thermally stabilized polymer composition as above described may further comprise at least one optional additional component selected from the group of fillers, reinforcing agents, fiberglass, lubricant agents, pigments, polymers other than the semi-aromatic polyamide, antioxidants, UV absorbers and light stabilizers, metal deactivators, phosphites and phosphonites, peroxide degraders, polyamide stabilizers, basic costabilizers, nucleating agents, and carbodiimmides.
  • the optional additional component is selected from the group of fiberglass, lubricant agents, aliphatic polyamides and nucleating agents.
  • the amount of flame retardant and stabilizer combined agent comprised in the composition according to the invention is advantageously of at least 1 wt. %, preferably of at least 2 wt.% and more preferably of at least 5 wt. % based on the total weight of the composition. Besides, this amount is advantageously of at most 30 wt. %, preferably of at most 20 wt. % and more preferably of at most 15 wt. %.
  • the flame retarded and thermally stabilized composition comprises fiberglass as reinforcing agent.
  • fiberglass is advantageously present in an amount of at least 30 wt. %, preferably of at least 45 wt. % and more preferably of at least 50 wt. % based on the total weight of the composition.
  • fiberglass is advantageously present in an amount of at most 90 wt. %, preferably of at most 80 wt. % and more preferably of at most 70 wt. % based on the total weight of the composition.
  • the components of the flame retardant and stabilizer combined agent along with and the optional additional components may be incorporated into the aromatic polyamide by a variety of different methods and procedural steps.
  • the present invention also relates a shaped article comprising the flame retarded and thermally stabilized polymer composition as previously described.
  • the shaped article according to the invention is advantageously an electric or an electronic part.
  • LXEF ® 6002, nucleated MXD6 polyamide derived from m-xylylene diamme and adipic acid (2) Exolit ® OP 1312 (Clariant), flame retardant and stabilizer combined agent comprising a metal phosphinate, a nitrogen synergist and zinc borate. (3) Exolit ® OP 1311 (Clariant), flame retardant agent comprising a metal phosphinate and a nitrogen synergist. (4) Exolit ® OP 1230 (Clariant), flame retardant agent comprising a metal phosphinate.
  • Example 1 a polymer composition according to the invention was prepared by compounding components (1), (2), (5) in the ratio given in Table 1.
  • two other polymer compositions were prepared by separately compounding components (1), (3), (5) (Comparative Example 2) and components (1), (4), (5) (Comparative Example 3), as given in Table 1.
  • Polymer components were compounded by means of a 25 mm Berstorff ® Twin Screw Extruder using identical operating conditions for comparability (temperature profiles, screw geometry, feeding modalities, etc.).
  • Example 1 The polymer composition of Example 1 (according to the invention), the polymer compositions according to Comparative Examples 2 and 3 and polymer composition LXEF ® 1521 0008 (i.e. halogenated flame retarded MXD6 composition comprising 50 wt. % of fiberglass, commercially available from Solvay Advanced Polymers L.L.C.) were tested and classified for the flame retardancy, on the basis of the UL 94 (Underwriters Laboratories) test. These compositions were also tested and classified for their thermal stability on the basis of their degradation onset temperature (determined by Thermo Gravimetric Analysis, TGA) and their molding behavior, in particular their tendency to discoloration and out gassing. The results of these tests are reported in Table 2.
  • TGA Thermo Gravimetric Analysis
  • TGA tests were carried out by means of a Universal V2.60 TA Instruments equipment. A sample having a size in the range 19 to 35 mg was placed into a tared TGA sample pan which was attached to a sensitive microbalance assembly. The sample holder portion of the TGA balance assembly was subsequently placed into a high temperature furnace. The balance assembly measured the initial sample weight at room temperature and then continuously monitored the losses in sample weight as heat was applied to the sample. TGA tests were run in a heating mode at a controlled heating rate. Typical weight loss profiles were analyzed for the amount or percent of weight loss at any given temperature. The degradation onset temperature is that measured at the intersection of the two lines that are tangent, respectively, to the flat portion of the weight loss curve (before degradation) and to its point of inflection.
  • the invented polymer composition has better flame resistance (UL 94 V0 at 1.6 mm) and/or improved thermal stability/mold ability in comparison with the halogenated and non halogenated flame retarded MXD6 compositions prepared and tested for comparative purposes.

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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

L'invention concerne une composition polymère ignifuge thermiquement stabilisée comprenant: (i) un polymère thermoplastique et (ii) un agent combiné constitué d'un élément ignifuge et d'un élément stabilisateur. Cet agent combiné comprend: en tant que composant (A), un élément ignifuge sélectionné dans le groupe comprenant: un sel phosphinique de formule (I), un sel diphosphinique de formule (II), des polymères de formule (I), des polymères de formule (II) et des mélanges de ceux-ci. Cet agent combiné est caractérisé en ce que: R1, R2 sont identiques ou différents et désignent: alkyle C1-C, linéaire ou ramifié, ou aryle; R3 désigne alkylène C1-C10, linéaire ou ramifié, arylène C6-C10, alkylarylène ou arylalkylène; M désigne Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K, ou une base d'azote protonée; m est compris entre 1 et 4; n est compris entre 1 et 4, x est compris entre 1 et 4. L'agent combiné comprend: en tant que composant (B), un élément synergique ignifuge sélectionné dans le groupe comprenant des éléments synergiques contenant de l'azote et des éléments synergiques contenant du phosphore/azote; en tant que composant (C), un élément de stabilisation thermique sélectionné dans le groupe comprenant: un oxyde basique ou emphotérique, un hydroxyde, un carbonate, un silicate, un borate, un stannate, un oxyde/hydroxyde mélangé, un oxyde/hydroxyde/carbonate, un hydroxyde/silicate, un hydroxyde/borate, ou un mélange de ceux-ci; éventuellement, en tant que composant (D), un phosphonite; éventuellement, en tant que composant (E), un ester ou un sel d'acide cireux de Montan; éventuellement, en tant que composant (F), un N,N'-bispipéridinyl-1,3-benzènedicarboxamide et/ou N,N'-bis(2,2,6,6-tétraméthyl-4-pipéridinyl)-1,3-benzène-dicarboxamide. La composition polymère étant caractérisée en ce que: le polymère thermoplastique (i) désigne un polyamide semi-aromatique comprenant des unités récurrentes dérivées d'un composant d'acide dicarboxylique comprenant au moins un acide dicarboxylique aliphatique et un composant diamine comprenant au moins une diamine aromatique. L'invention concerne également un article formé comprenant cette composition.
PCT/US2005/029791 2005-08-22 2005-08-22 Composition polymere ignifuge presentant une stabilite thermique accrue WO2005121234A2 (fr)

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PCT/US2005/029791 WO2005121234A2 (fr) 2005-08-22 2005-08-22 Composition polymere ignifuge presentant une stabilite thermique accrue
IT001614A ITMI20061614A1 (it) 2005-08-22 2006-08-10 Composizio0ne polimerica resa ignifuca con migliorata stabilita' termica
BE2006/0431A BE1020167A3 (fr) 2005-08-22 2006-08-16 Composition polymere ignifugee avec amelioration de la stabilite thermique.
FR0607329A FR2900409B1 (fr) 2005-08-22 2006-08-16 Composition polymere ignifugee avec amelioration de la stabilite thermique
CH01327/06A CH696700A5 (fr) 2005-08-22 2006-08-18 Composition polymère ignifugée avec amélioration de la stabilité thermique.

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EP1950238A3 (fr) * 2008-02-22 2008-09-03 Solvay Advanced Polymers, L.L.C. Composition de polymère résistant aux flammes avec stabilité de couleur améliorée
WO2008105616A1 (fr) * 2007-02-26 2008-09-04 Kolon Fashion Material, Inc. Fil de nylon, un tissu tricoté biface comprenant le fil de nylon et sur leurs procédés de production
EP1995280A1 (fr) * 2006-03-17 2008-11-26 Mitsubishi Engineering-Plastics Corporation Formule et moulage de résine polyamide ignifugeante
WO2010002403A1 (fr) * 2008-07-02 2010-01-07 E. I. Du Pont De Nemours And Company Composition de résine de polyamide semi-aromatique ignifuge comprenant du stannate de zinc, et objets obtenus à partir de cette composition
FR2934410A1 (fr) * 2008-07-28 2010-01-29 Nexans Composition ceramisable pour cable d'energie et/ou de telecommunication
JPWO2010073595A1 (ja) * 2008-12-22 2012-06-07 三井化学株式会社 難燃性ポリアミド組成物
WO2012064965A3 (fr) * 2010-11-10 2013-03-28 E. I. Du Pont De Nemours And Company Composition ignifuge de polyamide sans halogène
US8541489B2 (en) 2008-07-01 2013-09-24 E I Du Pont De Nemours And Company Flame resistant semiaromatic polyamide resin composition including zinc stannate, and articles therefrom
CN103819473A (zh) * 2013-07-01 2014-05-28 江阴摩尔化工新材料有限公司 一种甘脲树脂及其制备方法
WO2016089678A1 (fr) * 2014-12-01 2016-06-09 Ticona Llc Composition polymère présentant une performance d'inflammabilité améliorée
CN109320910A (zh) * 2018-08-21 2019-02-12 中国地质大学（武汉） 金属有机框架结构包裹聚磷酸铵阻燃剂的制备方法及应用
CN110272622A (zh) * 2018-03-14 2019-09-24 财团法人纺织产业综合研究所 阻燃塑胶粒及阻燃片材
WO2022214755A1 (fr) 2021-04-08 2022-10-13 Arkema France Compositions de polyamide ignifuges, leurs utilisations et leurs procedes de preparation
WO2022214754A1 (fr) 2021-04-08 2022-10-13 Arkema France Compositions de polyamide ignifuges, leurs utilisations et leurs procedes de preparation
WO2023099845A1 (fr) 2021-12-02 2023-06-08 Arkema France Composition de polyamide isolante et ignifugee pour recouvrement de barre d'interconnexion de batterie electrique
EP4241977A1 (fr) 2022-03-10 2023-09-13 Arkema France Structure tubulaire multicouche ignifugée pour le refroidissement de batteries de véhicule électrique ou de système de stockage stationnaire de l'énergie
WO2023209293A1 (fr) 2022-04-28 2023-11-02 Arkema France Compositions de polyamide ignifuge ductile et leur utilisation notamment pour application ferroviaire

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FR2954773B1 (fr) 2009-12-24 2013-01-04 Arkema France Polyamide semi-aromatique, son procede de preparation, composition comprenant un tel polyamide et leurs utilisations
FR2976946B1 (fr) 2011-06-24 2014-01-24 Arkema France Composition comprenant un polyamide semi-aromatique et ses utilisations, notamment pour un reflecteur a diode electroluminescente

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US7294661B2 (en) * 2003-10-03 2007-11-13 E.I. Du Pont De Nemours And Company Flame resistant aromatic polyamide resin composition and articles therefrom
CA2549487A1 (fr) * 2003-12-19 2005-07-07 Rhodia Engineering Plastics S.R.L. Composition ignifugee a base de matrice thermoplastique

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EP1995280A4 (fr) * 2006-03-17 2012-08-01 Mitsubishi Eng Plastics Corp Formule et moulage de résine polyamide ignifugeante
EP1995280A1 (fr) * 2006-03-17 2008-11-26 Mitsubishi Engineering-Plastics Corporation Formule et moulage de résine polyamide ignifugeante
WO2008105616A1 (fr) * 2007-02-26 2008-09-04 Kolon Fashion Material, Inc. Fil de nylon, un tissu tricoté biface comprenant le fil de nylon et sur leurs procédés de production
WO2009056583A2 (fr) * 2007-11-01 2009-05-07 Solvay Advanced Polymers, L.L.C. Composition polymère ignifuge à stabilité de couleur améliorée
WO2009056583A3 (fr) * 2007-11-01 2009-06-18 Solvay Advanced Polymers Llc Composition polymère ignifuge à stabilité de couleur améliorée
EP1950238A3 (fr) * 2008-02-22 2008-09-03 Solvay Advanced Polymers, L.L.C. Composition de polymère résistant aux flammes avec stabilité de couleur améliorée
US8541489B2 (en) 2008-07-01 2013-09-24 E I Du Pont De Nemours And Company Flame resistant semiaromatic polyamide resin composition including zinc stannate, and articles therefrom
JP2011526940A (ja) * 2008-07-02 2011-10-20 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー スズ酸亜鉛を含む耐燃性半芳香族ポリアミド樹脂組成物、およびそれからの物品
EP2297236A1 (fr) 2008-07-02 2011-03-23 E. I. du Pont de Nemours and Company Composition de résine de polyamide semi-aromatique ignifuge comprenant du stannate de zinc, et objets obtenus à partir de cette composition
WO2010002403A1 (fr) * 2008-07-02 2010-01-07 E. I. Du Pont De Nemours And Company Composition de résine de polyamide semi-aromatique ignifuge comprenant du stannate de zinc, et objets obtenus à partir de cette composition
WO2010012932A1 (fr) * 2008-07-28 2010-02-04 Nexans Composition ceramisable pour cable d'energie et/ou de telecommunication
FR2934410A1 (fr) * 2008-07-28 2010-01-29 Nexans Composition ceramisable pour cable d'energie et/ou de telecommunication
JP5761998B2 (ja) * 2008-12-22 2015-08-12 三井化学株式会社 難燃性ポリアミド組成物
JPWO2010073595A1 (ja) * 2008-12-22 2012-06-07 三井化学株式会社 難燃性ポリアミド組成物
WO2012064965A3 (fr) * 2010-11-10 2013-03-28 E. I. Du Pont De Nemours And Company Composition ignifuge de polyamide sans halogène
CN103819473A (zh) * 2013-07-01 2014-05-28 江阴摩尔化工新材料有限公司 一种甘脲树脂及其制备方法
WO2016089678A1 (fr) * 2014-12-01 2016-06-09 Ticona Llc Composition polymère présentant une performance d'inflammabilité améliorée
CN110272622A (zh) * 2018-03-14 2019-09-24 财团法人纺织产业综合研究所 阻燃塑胶粒及阻燃片材
CN109320910A (zh) * 2018-08-21 2019-02-12 中国地质大学（武汉） 金属有机框架结构包裹聚磷酸铵阻燃剂的制备方法及应用
CN109320910B (zh) * 2018-08-21 2019-10-18 中国地质大学（武汉） 金属有机框架结构包裹的聚磷酸铵阻燃剂的制备方法及应用
FR3121681A1 (fr) 2021-04-08 2022-10-14 Arkema France Compositions de polyamide ignifuges, leurs utilisations et leurs procedes de preparation
WO2022214754A1 (fr) 2021-04-08 2022-10-13 Arkema France Compositions de polyamide ignifuges, leurs utilisations et leurs procedes de preparation
WO2022214755A1 (fr) 2021-04-08 2022-10-13 Arkema France Compositions de polyamide ignifuges, leurs utilisations et leurs procedes de preparation
FR3121680A1 (fr) 2021-04-08 2022-10-14 Arkema France Compositions de polyamide ignifuges, leurs utilisations et leurs procedes de preparation
WO2023099845A1 (fr) 2021-12-02 2023-06-08 Arkema France Composition de polyamide isolante et ignifugee pour recouvrement de barre d'interconnexion de batterie electrique
FR3129943A1 (fr) 2021-12-02 2023-06-09 Arkema France Composition de polyamide isolante et ignifugee pour recouvrement de barre d’interconnexion de batterie electrique
EP4241977A1 (fr) 2022-03-10 2023-09-13 Arkema France Structure tubulaire multicouche ignifugée pour le refroidissement de batteries de véhicule électrique ou de système de stockage stationnaire de l'énergie
WO2023170366A1 (fr) 2022-03-10 2023-09-14 Arkema France Structure tubulaire multicouche ignifugee pour le refroidissement de batteries de vehicule electrique ou de systeme de stockage stationnaire de l'energie
FR3133336A1 (fr) 2022-03-10 2023-09-15 Arkema France Structure tubulaire multicouche ignifugee pour le refroidissement de batteries de vehicule electrique ou de systeme de stockage stationnaire de l’energie
WO2023209293A1 (fr) 2022-04-28 2023-11-02 Arkema France Compositions de polyamide ignifuge ductile et leur utilisation notamment pour application ferroviaire
FR3135085A1 (fr) 2022-04-28 2023-11-03 Arkema France Compositions de polyamide ignifuge ductile et leur utilisation notamment pour application ferroviaire

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BE1020167A3 (fr) 2013-06-04
CH696700A5 (fr) 2007-10-15
ITMI20061614A1 (it) 2007-02-23
WO2005121234A3 (fr) 2006-03-02
FR2900409B1 (fr) 2010-03-19

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