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    • 专利摘要:
    A flame retarded and heat stabilized polymeric composition comprising (i) a semiaromatic polyamide comprising repeating units derived from a dicarboxylic acid component including at least one dicarboxylic acid and a diamine component including at least one aromatic diamine, and (ii) a combined agent flame retardant and stabilizer comprising a phosphinic and / or disphosphinic salt flame retardant, a flame retardant synergist, and a thermal stabilizer.
    公开号:BE1020167A3
    申请号:E2006/0431
    申请日:2006-08-16
    公开日:2013-06-04
    发明作者:Glenn P Desio；Trail Timberlake
    申请人:Solvay Advanced Polymers Llc；
    IPC主号:
    专利说明:

    Flame-resistant polymer composition with improved thermal stability
    The present invention relates to a thermally stable flame retarded polymer composition comprising a semi-aromatic polyamide derived from at least one aromatic diamine. The invention also relates to a shaped article comprising said polymer composition.
    Semi-aromatic polyamides (such as those derived from phthalic acids and aliphatic diamines, that is polyphthalamides, or those derived from aromatic diamines and aliphatic diacids) are polymers having excellent mechanical, physical and which makes them useful for a wide range of different applications.
    For certain end-uses, it is desirable that compositions based on these semi-aromatic polyamides, in particular those derived from aromatic diamines and aliphatic diacids, be flame retarded so as to comply with the UL 94 V-0 standard in order to have high degree of fire resistance.
    A method generally used to impart polymers with fire resistance involves the incorporation of halogenated flame retardants.
    However, particularly in the case of high melting semi-aromatic polyamides, the halogenated flame retardants tend to thermally decompose at the molding temperature. The halogenated degradation products corrode the surfaces of the mixing extruder and give the molded articles a mediocre surface appearance.
    In particular, the halogenated flame retardant compositions of the prior art based on a polyamide derived from aromatic diamines are rather unstable during the melt processing, which results in degradation and / or decomposition problems such as discoloration, gas evolution, efflorescence on the surface of the molded article and degradation of the molecular weight of the polymer matrix.
    It would be highly desirable that such flame retarded compositions, particularly those based on polyamides derived from adipic acid and m-xylylenediamine (i.e. MXD6 polyamides), not only comply with the standard UL 94 V-0, but also have excellent stability and moldability. These flame retarded and thermally stabilized MXD6 compositions, if available, would be useful for a wide range of different applications such as, for example, the molding of electrical and electronic parts.
    Several halogen-free flame retardants and several flame retarded polymeric halogen-free compositions are known in the art. For example, US 3,900,444 discloses flame resistant thermoplastic polyesters containing halogen-free flame retardants based on alkali metal phosphinates. The use of metal phosphinates as halogen-free flame retardants for, above all, amorphous polyamides is described in US 4,036,811. Synergistic combinations of metal phosphinates with certain nitrogen-containing compounds are described in US Pat. No. 4,036,811. described in US 6,365,071. These synergistic combinations are generally more effective than metal phosphinates alone, with regard to many thermoplastic polymers (for example polyolefins, polystyrene, halogenated polymers, polyacetals, polycarbonates, polysulfones, polyetherketones, polyamides, polyesters), preferably engineering plastics and in particular polyesters. WO 0066658 discloses the use of carbodiimides, isocyanates and isocyanurates for the purpose of stabilizing polymer molding compositions containing phosphorus flame retardants.
    However, as indicated in document US 2004/0227130, when halogen-free phosphorus-containing flame retardants are used specifically in combination with polyamides, the action of the stabilizers described so far has been found insufficient in particularly to suppress the effects occurring during the melt processing, such as discoloration and molecular weight degradation.
    If halogen-free flame retardant polyamide compositions in which 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 Pat. 2005/014874), the same can not be said of halogen-free flame retardant polyamide compositions in which the polyamide is a semi-aromatic polyamide derived from at least one aromatic diamine, such as MXD6 polyamides. US 6,255,371 and US 2005/014874 disclose halogen-free flame retardant compositions based on thermoplastic polymers, wherein the thermoplastic polymer may be MXD6 polyamides or polyamides including an aromatic diamine such as xylylenediamine and wherein Flame retardant is a metal phosphinate in combination, possibly or not, with a nitrogen synergist. However, the prior art remains silent about the thermal stability of such polymeric compositions as well as the degradation problems that can be expected during their melt processing.
    On the other hand, flame retardant and stabilizing combined agents have been described in US 2004/0227130 for a wide range of different thermoplastic polymers, but these agents are reported to be effective, particularly for aliphatic polyesters and polyamides such as nylon-6 and nylon 6-6.
    From the above discussion, it appears that further research is needed in this field, in particular in order to understand the behavior of the flame retardants, the thermal stability and the moldability of flame retardant polyamide compositions free of halogen-based aromatic polyamides derived from at least one aromatic diamine.
    In particular, an object of the present invention is to provide a flame retardant polyamide composition based on a semi-aromatic polyamide comprising repeating units derived from a dicarboxylic acid component including at least one aliphatic dicarboxylic acid and a diamine component including at least one an aromatic diamine, wherein said composition, besides conforming to UL 94 V-0 for a high degree of fire resistance, also has excellent thermal stability so as to be molded without encountering any of the problems degradation and / or discoloration mentioned above.
    Therefore, the invention provides a flame retarded and thermally stabilized polymeric composition comprising (i) a thermoplastic polymer and (ii) a flame retardant and stabilizing 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 (Π), polymers of the formula (I), polymers of the formula (Π) and mixtures thereof,
    do
    wherein: R1, R2 are the same or different and are C1-C6-alkyl, linear or branched, or aryl; R3 is linear or branched C1-C10-alkylene, C6-C10-arylene, alkylarylene or arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, U, Na, K, or a protonated nitrogenous base; m is a number from 1 to 4; n is a number from 1 to 4; and x is a number from 1 to 4; as component (B), a flame retardant synergist selected from the group consisting of nitrogen-containing synergists and phosphorus / nitrogen-containing synergists as a component ( C), a thermal stabilizer selected from the group consisting of a basic or amphoteric oxide, a hydroxide, a carbonate, a silicate, a borate, a stannate, an oxide / hydroxide mixture, oxide / hydroxide / carbonate, hydroxide / silicate, hydroxide / borate, or a mixture thereof optionally as component (D), a phosphonite of the structure R- [P (ORi) 2] m (I) wherein R is a mono- or polyvalent aliphatic, aromatic organic radical or heteroaromatic, and Ri is a compound of the structure (Π)
    OD
    where the two radicals Ri form a bridging group of the structure (ΙΠ)
    (in) wherein: A is a direct bond, O, S, a Cl-18-alkylene (linear or branched), or Cl-18-alkylidene (linear or branched); R2, independently of one another, are Cl-8-alkyl (linear or branched), Cl-12-alkoxy, or C5-12-cycloalkyl; and n is a number from 0 to 5, and m is a number from 1 to 4, optionally as component (E), an ester or an acid salt of lignite wax, optionally as a component (F ), a N, N'-bis-piperidinyl-1,3-benzenedicarboxamide and / or a N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide, said polymer composition characterized in that the thermoplastic polymer (i) is a semi-aromatic polyamide comprising repeating units derived from a dicarboxylic acid component including at least one aliphatic dicarboxylic acid and a diamine component including at least one aromatic diamine.
    The aromatic polyamide composition of the invention provides reduced discoloration during the melt processing, reduced degradation together with complete retention of flame retardancy.
    M is preferably calcium, aluminum or zinc.
    The protonated nitrogenous bases are preferably the protonated bases of ammonia, melamine, triethanolamine, in particular NH4 * R1 and R2, which may be identical or different, are preferably a linear or branched C1-C6-alkyl group, and / or phenyl.
    R1 and R2, which are identical or different, are particularly preferably a methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl group.
    R3 is preferably methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, or n-dodecylene.
    Another preferred meaning of R3 is phenylene or naphthylene.
    Suitable phosphinates have been described in US 6,365,071 specifically incorporated herein by reference. Particularly preferred phosphinates are aluminum phosphinates, calcium phosphinates, and zinc phosphinates.
    Synergistic combinations of the specified phosphinates with nitrogen-containing compounds which have a more effective action as flame retardants than phosphinates alone in many polymers (US 6,365,071, US 6,207,736, US 6,509,401) are also in accordance with the invention.
    The flame resistance action of phosphinates can be improved by combining with other flame retardants, preferably nitrogen-containing synergists, or phosphorus / nitrogen flame retardants. The component-containing nitrogen-containing synergist (B) is represented by the formulas (ΙΠ) to (HIV), or a mixture thereof ([[
    wherein R5 to R7 are hydrogen, C1-C8-alkyl, C5-C16-cycloalkyl or -alkylcycloalkyl, optionally substituted with a hydroxyl or Cl-function; C4-hydroxyalkyl, C2-C8-alkenyl, C1-C8-alkoxy, -acyl, -acyloxy, C6-C12-aryl or -arylalkyl, -OR8, or -N (R8) R9, or an N-alicyclic system or N-aromatic; R8 is hydrogen, C1-C8-alkyl, C5-C16-cycloalkyl or -alkylcycloalkyl, optionally substituted with hydroxyl or C1-C4-hydroxyalkyl, C2-C8-alkenyl , C1-C8-alkoxy, -acyl, -acyloxy, or C6-C12-aryl or -arylalkyl; R9-R13 are the same as for R8, or alternatively -O-R8; m and n independently one of other, are 1,2,3, or 4; X is an acid which forms adducts with triazine compounds (ΙΠ), or an oligomer ester of tris (hydroxyethyl) isocyanurate with aromatic polycarboxylic acids.
    The nitrogen-containing synergists preferably include benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, dicyandiamide, guanidine, carbodiimides.
    Nitrogen-containing synergists preferably include condensation products of melamine. For example, the condensation products of melamine are melem, melam, or melon, or compounds of this type with a higher level of condensation, or otherwise a mixture thereof, and for example, can be prepared by the process described in US 5,985,960.
    Phosphorus / nitrogen containing synergists may include reaction products of melamine with phosphoric acid or with condensed phosphoric acids, or include reaction products of melamine condensation products with acid. phosphoric acid or condensed phosphoric acids, or otherwise comprise a mixture of the specified products.
    Reaction products with phosphoric acid or with condensed phosphoric acids are compounds that occur through a reaction of melamine or condensed melamine compounds, such as melam, melem, or melon etc. ., with phosphoric acid. By way of example, there may be mentioned dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate, and mixed polysels, for example those described in US Pat. US 6,121,445 and US 6,136,973.
    The phosphorus / nitrogen-containing synergist may also be ammonium hydrogen phosphate, ammonium dihydrogenphosphate, or ammonium polyphosphate.
    Preferably, the phosphorus / nitrogen-containing synergist of component (B) is at least one nitrogen-containing phosphate selected from the group consisting of melamine polyphosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium polyphosphate.
    Additives may be added to the phosphinates alone or in combination with phosphorus / nitrogen flame retardants, the examples of these additives being: 1. Antioxidants 1.1 Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 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-a-methylcyclohexyl) -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- (1-methylundec-1'-yl) phenol, 2,4-dimethyl-6-one 1-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (r-methyltridec-r-yl) phenol and mixtures thereof.
    1.2 Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
    1.3 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, with (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
    1.4 Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E).
    1.5 Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl) 3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2-methylphenol) , 6-dimethyl-4-hydroxyphenyl) disulfide.
    1.6 Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4] methyl-6- (α-methylcyclohexyl) phenol, 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2 2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2, 6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol with [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) bu) tyrate], (2-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl] 4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-2-hydroxyphenyl) butane bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
    1.7 O-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, 4-hydroxy-3,5-dimethylbenzylmercaptoacetate octadecyl, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, Ie (3,5-di-tert) butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
    1.8 Hydroxybenzyl malonates, for example dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate dioctadecyl, didodecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethylbutyl) phenyl] 2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    1.9 Aromatic hydroxybenzyl compounds, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di -tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
    Triazine compounds, for example 2,4-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) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di -tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 2,4,6-tris (3,5 1-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5- triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    1-Benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4 dioctadecyl dihydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
    1.12Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    1.13 Esters of P- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, hexanol 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-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
    1.14 Esters of P- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, hexanol 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-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
    1.15Esters of p- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example 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-1-phospha-2,6,7-trioxabicyclo [2.2.2 ]octane.
    1, 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, for example 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-1-phospha-2,6,7-trioxabicyclo [2.2.2 ]octane.
    1.17Amides of p- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
    2. UV absorbers and light stabilizers 2.1 2- (2'-Hydroxyphenyl) benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di- tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) ) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) 5-chlorobenzotriazole, 2- (3, -sec-butyl-5, -tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, a mixture of 2- (3'-dihydroxyphenyl) benzotriazole, tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2 ' hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2, -hydroxy-5 '- (2-methoxycarbonyl-ethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert) -butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2 ( 3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- benzotriazol-2-ylphenol]; the product of transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; [R-CH 2 CH 2 -COO (CH 2) 3] 2-, where R = 3, -tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
    2.2 Hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and the 2'-hydroxy-4 derivative, 4'-dimethoxy.
    2.3 Substituted or unsubstituted benzoic acid esters, eg 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5 2,4-di-tert-butylphenyl-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4- octadecyl hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
    2.4 Acrylates, for example α-cyano-β, β-diphenylacrylate or α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, α-cyano-β-methyl-p-methoxycinnamate methyl or butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carbonrethoxy-β-cyanovinyl) -2-methylindoline.
    2.5 Nickel compounds, for example 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol] nickel complexes, such as the 1: 1 or 1: 2 complex, with or without ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as those of the methyl ester or the ethyl ester, of the 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole , with or without additional ligands.
    2.6 Hindered amines, eg (2,2,6,6-tetramethylpiperidyl) sebacate, (2,2,6,6-tetramethylpiperidyl) succinate, (1,2,6,6-pentamethylpiperidinyl) sebacate, (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-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6 dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2 3,4-butanetetrazoate, 1,1- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy- 2,2,6,6-tetramethyl-piperidine, (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazas-piro [4.5] decane-2,4-dione, at (1-oc) tyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, the condensate of N, N'-bis (2,2,6,6 tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-di- (4-n-butylamino) 2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the condensate of 2-chloro-4,6-di (4-n- butylamino-1,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9, 9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione.
    2.7 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 o- and p-ethoxy-disubstituted oxanilides.
    2.8 2- (2-Hydroxyphenyl) -1,3,5-triazines, such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2- 4-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) 1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-yl) octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.
    3. Deactivators of metals, for example, Ν, Ν'-diphenyloxalamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di- tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, Ν, Ν'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.
    4. Phosphites and phosphonites, eg 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-di-tert- butyl-6-methylphenyl) pentaerythritol diphosphite, (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite, 6- isooctyloxy-2,4,8,10-tetra-tert-butyl-12-H-dibenzo [d, g] -1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert -butyl-1-methyl-2-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocine, (2,4-di-tert-butyl-6-methyl-phenyl) methyl phosphite, (2,4-di-tert) butyl-6-methylphenyl) ethyl phosphite.
    5. Peroxide-Degrading Agents, for example β-thiodipropionic acid esters, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, 2-mercaptobenzimidazole zinc salt, zinc dibutyldithiocarbamate , dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.
    6. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds; the manganese salts divalent.
    7. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metals, higher fatty acids, examples of which are Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate, or tin pyrocatecholate.
    8. Nucleating agents, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
    9. Fillers and reinforcing agents, eg calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides, and metal hydroxides, carbon black, graphite.
    10. Other additives, for example plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
    The thermal stabilizer corresponding to the 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, hydroxide manganese, zinc borate, basic zinc silicate, zinc stannate, and / or zinc hydroxide.
    Preferably, the thermal stabilizer is zinc borate, magnesium hydroxide, zinc hydroxide, dihydrotalcite, and / or boehmite. More preferably, the thermal stabilizer is zinc borate.
    The zinc borate useful for the present invention is preferably anhydrous zinc borate with less than 0.2% by weight water (as described in US 5,204,400) and, more preferably, with no content. in measurable water such as zinc borate XPI-187 from US Borax.
    The phosphonites of the R- [P (ORO2) m (I) structure are suitable as component D, where R is a mono- or polyvalent aliphatic, aromatic or heteroaromatic organic radical, and Ri is a compound of the structure (Π )
    (H) where the two radicals Rj form a bridging group of the structure (ΙΠ)
    Where A is a direct bond, O, S, a Cl-18-alkylene group (linear or branched), or Cl-18-alkylidene (linear or branched), where R2 independently of one another, are a Cl-8-alkyl (linear or branched), Cl-12-alkoxy, or C5-12-cycloalkyl group, and n is a number from 0 to 5, and m is a number from 1 to 4.
    The preferred radicals are: R is C4-18-alkyl (linear or branched), C4-18-alkylene (linear or branched), C5-12-cycloalkyl, C5-12-cycloalkylene, C6-24-aryl or -heteroaryl, C6-24-arylene or heteroarylene, which may also have additional substitution;
    R 1 is a group of the structure (Π) or (III), wherein R 2, independently of one another, are Cl-8-alkyl (linear or branched), C 1-8 -alkoxy, cyclohexyl; A is a direct bond, O, a Cl-8-alkylene (linear or branched), Cl-8-alkylidene (linear or branched), and n is a number from 0 to 3, and m is a number from 1 to 3 .
    Particularly preferred radicals are: R cyclohexyl, phenyl, phenylene, biphenyl radicals;
    R 1 a group of the structure (Π) or (ΙΠ), wherein R 2, independently of one another, are Cl-8-alkyl (linear or branched), C 1-8 -alkoxy, cyclohexyl; A is a direct bond, O, a Cl-6-alkylidene (linear or branched), and n is a number from 1 to 3, and m is 1 or 2.
    Mixtures of compounds according to the preceding claims in combination with phosphites of the formula (IV) are also claimed, wherein R 1 is as defined above P (OR 1) 3 (IV).
    Particular preference is given to compounds which, on the basis of the preceding claims, are prepared by means of a Friedel-
    Crafts of an aromatic or heteroaromatic system, such as benzene, biphenyl or diphenyl ether, with phosphorus trihalides, preferably phosphorus trichloride, in the presence of a Friedel-Crafts catalyst, such as aluminum, zinc chloride, iron chloride, etc., and a subsequent reaction with the phenols underlying the (Π) and (ΙΠ) structures. The mixtures with the phosphites produced in the specified reaction sequence from an excess of phosphorus trihalide and from the phenols described above are expressly also covered by the invention.
    Among this group of compounds, the preference is in turn given to the structures (V) and (VI) below:
    (V)
    (VII
    where n can be 0 or 1, and where these mixtures can also optionally include proportions of the compound (VII) or (HIV): (VII)
    (VIII)
    The esters or salts of the long-chain aliphatic carboxylic acids (fatty acids), which generally have chain lengths of from 04 to 40, are suitable as an example of component (E). The esters include reaction products of the specified carboxylic acids with familiar polyhydric alcohols, eg ethylene glycol, glycerol, trimethylolpropane, or pentaerythritol. The alkali metal or alkaline earth metal salts, or the aluminum salts and the zinc salts of the specified carboxylic acids are in particular used.
    Component (E) preferably comprises esters or salts of stearic acid, for example glycerol monostearate or calcium stearate.
    Component (E) preferably comprises reaction products of the lignite wax acids with ethylene glycol.
    The reaction products preferably comprise a mixture of mono- and di- (ethylene glycol) acid esters of lignite wax, lignite wax acids and ethylene glycol.
    The component (E) preferably comprises reaction products of the lignite wax acids with a calcium salt.
    Particularly preferably, the reaction products comprise a mixture of mono- and di (1,3-butanediol) acid esters of lignite wax, lignite wax acids, 1,3-butanediol, montanate calcium, and calcium salt.
    The carboxylic amides (ester) are suitable as component (F).
    Component (F) preferably comprises a derivative of an aromatic di- or tricarboxylic amide (ester).
    The derivative preferably comprises N, N'-bis-pipiperidinyl-1,3-benzene dicarboxamide.
    The derivative particularly preferably comprises N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide.
    The quantitative proportions of components (A), (B), and (C) in the flame retardant and stabilizer combined agent are essentially dependent on the intended application area, and may vary within wide limits. Depending on the area of application, the combined flame retardant and stabilizer 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. % 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 stabilizing combined agent preferably comprises from 50 to 90% by weight of the component (A), from 0 to 50% by weight of the component (B), from 1 to 20% by weight of the component (C), 0 to 5% by weight of component (D), 0 to 5% by weight of component (E), and 0.1 to 5% by weight of component (F).
    The flame retardant and stabilizing 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 flame retardant and stabilizing combined agent of the invention may also comprise carbodiimides.
    The aliphatic dicarboxylic acid used for the preparation of the semi-aromatic polyamide is advantageously chosen from the group comprising linear aliphatic α, ω-dicarboxylic acids and alicyclic dicarboxylic acids. It is possible to use a single acid or a mixture of acids. Preferably, the aliphatic dicarboxylic acid is linear and contains from 4 to 12 carbon atoms; more preferably it is an 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 thereof. Preferably, the aromatic diamine is m-xylylenediamine. The diamine component may further comprise at least one diamine selected from the group consisting of linear aliphatic diamines, alicyclic diamines, aromatic diamines other than xylylenediamines.
    If necessary, the semi-aromatic polyamide may further comprise copolymerized repeating units derived from at least one α-ω aminocarboxylic acid and / or at least one lactam.
    Preferably, the semi-aromatic polyamide comprises repeating 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 repeating units derived from adipic acid and m-xylylenediamine.
    Even more preferably, the semi-aromatic polyamide consists of repeating units derived from adipic acid and m-xylylenediamine.
    The semi-aromatic polyamides derived from adipic acid and m-xylylenediamine are commercially available under the trade name Polyamide IXEF® from SOLVAY ADVANCED POLYMERS L.L.C.
    The flame-retarded and heat-stabilized polymer composition as described above may further comprise at least one optional additional component chosen from the group comprising fillers, reinforcing agents, fiberglass, lubricating agents, pigments, polymers and the like. other than semi-aromatic polyamide, antioxidants, UV absorbers and light stabilizers, metal deactivators, phosphites and phosphonites, peroxide degrading agents, polyamide stabilizers, basic co-stabilizers , nucleating agents, and carbodiimmides.
    Preferably, the optional additional component is selected from the group consisting of fiberglass, lubricating agents, aliphatic polyamides and nucleating agents.
    The amount of flameproofing and stabilizing combined agent included in the composition according to the invention is advantageously at least 1% by weight, preferably at least 2% by weight and more preferably at least 5% by weight. weight based on the total weight of the composition. In addition, this amount is advantageously at most 30% by weight, preferably at most 20% by weight and more preferably at most 15% by weight.
    In some preferred embodiments of the present invention, the flame retarded and thermally stabilized composition comprises fiberglass as a reinforcing agent.
    In these embodiments, the glass fiber is preferably present in an amount of at least 30% by weight, preferably at least 45% by weight and more preferably at least 50% by weight based on the total weight of the composition. Further, the fiberglass is advantageously present in an amount of at most 90% by weight, preferably at most 80% by weight and more preferably at most 70% by weight based on the total weight of the composition.
    The components of the flame retardant and stabilizing combined agent and any additional components may be incorporated into the aromatic polyamide by a variety of different processes and process steps. For example, it is possible to incorporate the aforementioned components by mixing them in the polymer at an early stage: at the beginning or at the end of the polymerization / polycondensation of the polyamide, or in a subsequent mixing process. There are also processes in which the components of the flame retardant and stabilizing combined agent are added only later. One possibility is to dry mix the various components of the composition in a drum before mixing by extrusion. Finally, the components of the flame retardant and stabilizing combined agent can be applied to the polymer granules, which may have retained heat from the drying process.
    The present invention also relates to a shaped article comprising the flame-retarded and thermally stabilized polymer composition as previously described.
    The profiled article according to the invention is advantageously an electrical part or an electronic part.
    Examples
    Components used for Examples 1 to 3 (1) IXEF ® 6002, nucleated MXD6 polyamide derived from m-xylylene diamine and adipic acid.
    (2) Exolil ® OP 1312 (Clariant), a flame retardant combined agent and stabilizer comprising a metal phosphinate, a nitrogen synergist and zinc borate.
    (3) Exolil ® OP 1311 (Clariant), flame retardant comprising a metal phosphinate and a nitrogen synergist.
    (4) Exolil ® OP 1230 (Clariant), flame retardant comprising a metal phosphinate.
    (5) 983 EC ® Glass fibers, cut rods, dia 10 μηι, 4.5 mm long (Saint-Gobain Vetrotex America), fiberglass used as reinforcing agent.
    Preparation of polymer compositions
    For Example 1, a polymer composition according to the invention was prepared by mixing the components (1), (2), (5) according to the ratio shown in Table 1.
    For comparison purposes, two other polymeric compositions were prepared by separately mixing the components (1), (3), (5) (Comparative Example 2) and the components (1), (4), (5) (Example Comparative 3) as shown in Table 1.
    The polymeric components were mixed using a Berstorff ® 25 mm twin screw extruder using identical operating conditions to allow comparison (temperature profiles, screw geometry, feed modalities, etc.). The conditions of carrying out the mixing were defined in order to obtain a melting temperature of 280 ° C. at the level of the die.
    The components (1) to (4) were mixed together and then fed into the feed chute of the Berstorff ® twin screw extruder. The component (5) has been introduced into a separate feed device.
    Table 1 - Polymer Compositions
    Properties of polymer compositions
    The polymer composition of Example 1 (according to the invention), the polymer compositions according to Comparative Examples 2 and 3 and the polymer composition IXEF® 1521 0008 (that is to say the halogenated flame retarded MXD6 composition comprising 50% by weight). fiberglass weights, commercially available from Solvay Advanced Polymers LLC) were tested and classified for flame resistance, based on UL 94 (Underwriters Laboratories).
    These compositions were also tested and classified in terms of their thermal stability as a function of their degradation start temperature (determined by thermogravimetric analysis, ATG) and their molding behavior, in particular their tendency to discoloration and release. gas. The results of these tests are reported in Table 2.
    ATG analyzes were performed using equipment of the Universal V2.60 TA Instruments type.
    A sample ranging in size from 19 to 35 mg was placed in a calibrated ATG sample receptacle which was attached to a sensitive microbalance assembly. The portion of the sample holder of the ATG balance assembly was then placed in a high temperature oven. The scale assembly measured the initial weight of the sample at room temperature and continuously monitored the weight loss of the sample while applying heat thereto. ATG tests were performed in heating mode at a controlled heating rate. Typical weight loss profiles were analyzed to determine the amount or percentage of weight loss at any given temperature. The degradation start 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.
    Table 2 - Promoses of nutritional and dietary supplements
    From the previous examples, it is apparent that the invented polymer composition has better fire resistance (UL 94 VO at 1.6 mm), and / or improved thermal stability / moldability compared to flame retarded MXD6 compositions. halogenated and non-halogenated prepared and tested for comparison.
    权利要求:
    Claims (20)
    [1]
    A flame retarded and heat stabilized polymeric composition comprising (i) a thermoplastic polymer and (ii) a flame retardant and stabilizing 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 (Π), polymers of the formula (I), polymers of the formula (II) and mixtures thereof,

    [2]
    Flame-resistant and heat-stabilized polymer composition according to claim 1, characterized in that in component (A) M is calcium, aluminum or zinc.
    [3]
    3. Fireproof and heat stabilized polymer composition according to claim 1 or 2, characterized in that, in the component (A), R1 and R2, identical or different, are a linear or branched C1-C6-alkyl group, and / or phenyl.
    [4]
    4. Fireproof and heat stabilized polymer composition according to claim 3, characterized in that, in the component (A), R1 and R2, identical or different, are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
    [5]
    5. Fireproof and heat stabilized polymer composition according to any one of claims 1 to 4, characterized in that, in component (A), R3 is methylene, ethylene, n-propylene, isopropylene, n-butylene, tert- butylene, n-pentylene, n-octylene, or n-dodecylene.
    [6]
    6. Fireproof and heat stabilized polymer composition according to any one of claims 1 to 4, characterized in that, in component (A), R3 is phenylene or naphthylene.
    [7]
    A flame retarded and heat-stabilized polymeric composition according to any one of claims 1 to 6, characterized in that component (B) is a nitrogen-containing synergist represented by formulas (III) to (VUI), or a mixture of these (Hl)

    [8]
    A flame retarded and heat-stabilized polymeric composition according to any one of claims 1 to 6, characterized in that component (B) is a phosphorus / nitrogen-containing synergist, ie at least one phosphate containing at least one nitrogen selected from the group consisting of melamine polyphosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium polyphosphate.
    [9]
    A flame-retarded and heat-stabilized polymeric composition according to any one of claims 1 to 8, characterized in that the thermal stabilizer is zinc borate, magnesium hydroxide, zinc hydroxide, dihydrotalcite, and / or boehmite.
    [10]
    Flame-resistant and heat-stabilized polymer composition according to claim 9, characterized in that the thermal stabilizer is zinc borate.
    [11]
    11. fireproof and heat-stabilized polymer composition according to any one of claims 1 to 10, characterized in that, in the optional component (D): - R is C4-18-alkyl (linear or branched), C4-18 -alkylene (linear or branched), C5-12-cycloalkyl, C5-12-cycloalkylene, C6-24-aryl or -heteroaryl, C6-24-arylene or heteroarylene, which may also have additional substitution; R 1 is a group of the structure (Π) or (III), wherein R 2, independently of one another, are a Cl-8-alkyl (linear or branched), C 1-8 -alkoxy, cyclohexyl; - A is a direct bond, O, a Cl-8-alkylene (linear or branched), Cl-8-alkylidene (linear or branched), - n is a number from 0 to 3, and - m is a number of 1 at 3.
    [12]
    12. Fireproof and heat stabilized polymer composition according to any one of claims 1 to 11, characterized in that it comprises the component (D).
    [13]
    13. Fireproof and heat-stabilized polymer composition according to any one of claims 1 to 12, characterized in that the aliphatic dicarboxylic acid included in the dicarboxylic acid component of the semi-aromatic polyamide is linear and contains from 4 to 12 carbon atoms .
    [14]
    Flame-stabilized and thermally stabilized polymer composition according to any one of claims 1 to 13, characterized in that the aromatic diamine included in the diamine component of the semi-aromatic polyamide is meta-xylylenediamine, para-xylylenediamine or a mixture of these.
    [15]
    15. Fireproof and heat-stabilized polymer composition according to any one of claims 1 to 14, characterized in that the semi-aromatic polyamide comprises repeating units derived from at least one linear aliphatic dicarboxylic acid containing from 4 to 12 carbon atoms and at least one xylylenediamine.
    [16]
    16. The flame-retarded and heat-stabilized polymer composition according to claim 15, characterized in that the semi-aromatic polyamide comprises recurring units derived from adipic acid and m-xylylenediamine.
    [17]
    Fireproof and heat stabilized polymeric composition according to claim 16, characterized in that the semi-aromatic polyamide consists of repeating units derived from adipic acid and m-xylylenediamine.
    [18]
    18. Fireproof and thermally stabilized composition according to any one of claims 1 to 17, characterized in that it further comprises fiberglass as reinforcing agent.
    [19]
    The fire retardant and heat stabilized composition according to claim 18, characterized in that the fiberglass is present in an amount of at least 45% by weight and at most 70% by weight based on the total weight of the composition .
    [20]
    20. Profile article, characterized in that it comprises the flame retarded and heat-stabilized polymer composition according to any one of the preceding claims.
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    同族专利:
    公开号 | 公开日
    WO2005121234A3|2006-03-02|
    FR2900409A1|2007-11-02|
    WO2005121234A2|2005-12-22|
    FR2900409B1|2010-03-19|
    ITMI20061614A1|2007-02-23|
    CH696700A5|2007-10-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2004292532A|2003-03-26|2004-10-21|Asahi Kasei Chemicals Corp|Flame-retardant, reinforced polyamide resin composition|
    JP2004300189A|2003-03-28|2004-10-28|Asahi Kasei Chemicals Corp|Polyamide flame-retardant resin composition|
    WO2005033192A1|2003-10-03|2005-04-14|E.I. Dupont De Nemours And Company|Flame resistant aromatic polyamide resin composition and articles therefrom|
    WO2005061606A1|2003-12-19|2005-07-07|Rhodia Engineering Plastics S.R.L.|Fireproof composition based on thermoplastic matrix|
    DE10241126A1|2002-09-03|2004-03-25|Clariant Gmbh|Flame retardant-stabilizer combination for thermoplastic polymers|WO2007108202A1|2006-03-17|2007-09-27|Mitsubishi Engineering-Plastics Corporation|Flame retardant polyamide resin composition and molding|
    WO2008105616A1|2007-02-26|2008-09-04|Kolon Fashion Material, Inc.|Nylon yarn, two-way knitted farbric comprising the nylon yarn and method of manufacturing thereof|
    EP1950238A3|2008-02-22|2008-09-03|Solvay Advanced Polymers, L.L.C.|Flame resistant polymer composition with improved color stability|
    US8541489B2|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|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|Flame resistant semi-aromatic polyamide resin composition comprising zinc stannate and articles therefrom|
    FR2934410A1|2008-07-28|2010-01-29|Nexans|CERAMIZABLE COMPOSITION FOR POWER CABLE AND / OR TELECOMMUNICATION|
    KR101323507B1|2008-12-22|2013-10-29|미쓰이 가가쿠 가부시키가이샤|Flame-retardant polyamide composition|
    FR2954773B1|2009-12-24|2013-01-04|Arkema France|SEMI-AROMATIC POLYAMIDE, PROCESS FOR PREPARING THE SAME, COMPOSITION COMPRISING SUCH POLYAMIDE AND USES THEREOF|
    CN102464881A|2010-11-10|2012-05-23|杜邦公司|Halogen-free flame-retardant polyamide composition|
    FR2976946B1|2011-06-24|2014-01-24|Arkema France|COMPOSITION COMPRISING A SEMI-AROMATIC POLYAMIDE AND USES THEREOF, IN PARTICULAR FOR AN ELECTROLUMINESCENT DIODE REFLECTOR|
    CN103819473A|2013-07-01|2014-05-28|江阴摩尔化工新材料有限公司|Glycoluril resin and preparation method thereof|
    CN107001937A|2014-12-01|2017-08-01|提克纳有限责任公司|Polymer composition with improved fire resistance|
    TWI670365B|2018-03-14|2019-09-01|Taiwan Textile Research Institute|Fire-retardant plastic pellet and fire-retardant sheet|
    CN109320910B|2018-08-21|2019-10-18|中国地质大学（武汉）|The preparation method and application of the ammonium polyphosphate flame retardant of metal-organic framework package|
    法律状态:
    2014-02-28| RE| Patent lapsed|Effective date: 20130831 |
    优先权:
    申请号 | 申请日 | 专利标题
    PCT/US2005/029791|WO2005121234A2|2005-08-22|2005-08-22|Flame retarded polymer composition with improved thermal stability|
    US2005029791|2005-08-22|
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