WO2012146624A1 - Matières à mouler ignifugées - Google Patents

Matières à mouler ignifugées Download PDF

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Publication number
WO2012146624A1
WO2012146624A1 PCT/EP2012/057576 EP2012057576W WO2012146624A1 WO 2012146624 A1 WO2012146624 A1 WO 2012146624A1 EP 2012057576 W EP2012057576 W EP 2012057576W WO 2012146624 A1 WO2012146624 A1 WO 2012146624A1
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WIPO (PCT)
Prior art keywords
weight
molding compositions
acid
compositions according
thermoplastic molding
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PCT/EP2012/057576
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German (de)
English (en)
Inventor
Alexander KÖNIG
Florian Garlichs
Klaus Uske
Michael Roth
Matthias Pfeiffer
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Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to BR112013027454A priority Critical patent/BR112013027454A2/pt
Priority to JP2014506849A priority patent/JP2014517093A/ja
Priority to EP12716451.5A priority patent/EP2702102A1/fr
Priority to CN201280020075.5A priority patent/CN103492488A/zh
Publication of WO2012146624A1 publication Critical patent/WO2012146624A1/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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • 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
    • C08K3/02—Elements
    • C08K2003/026—Phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • thermoplastic polyamide A) 10 to 99.4 wt .-% of at least one thermoplastic polyamide
  • the invention relates to the use of the molding compositions according to the invention for the production of fibers, films and moldings and the moldings obtainable in this case.
  • the incorporation of red phosphorus in polymer melts exist due to the dust formation and phosphine development safety problems.
  • WO2007 / 042446 discloses combinations of melamine compounds (in particular melamine polyphosphate) as flame retardant combination for PA, which are in need of improvement in terms of flame retardancy properties few color settings accessible. It is an object of the present invention to provide flame-retardant PA molding compositions which have improved flame retardancy, glow-wire resistance and dyeability and meet the above-mentioned standard. At the same time, the mechanical properties should remain as far as possible.
  • the molding compositions of the invention contain 10 to 99.4, preferably 20 to 98 and in particular 25 to 90 wt .-% of at least one polyamide.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 1 10 to 240 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307.
  • Semicrystalline or amorphous resins having a weight average molecular weight of at least 5,000 e.g. U.S. Patents 2,071,250, 2,071,251, 2,130,523, 2,130,948, 2,241,322, 2,312,966, 2,512,606 and 3,393,210 are preferred.
  • Examples include polyamides derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam and polyamides obtained by reacting dicarboxylic acids with diamines.
  • dicarboxylic acids alkanedicarboxylic acids having 6 to 12, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used.
  • adipic acid, azelaic acid, sebacic acid, dodecanedioic acid and terephthalic and / or isophthalic acid may be mentioned as acids.
  • Suitable diamines are particularly alkanediamines having 6 to 12, especially 6 to 8 atoms of carbon and m-xylylenediamine (for example Ultramid ® X17 from BASF SE, a 1: 1 molar ratio of MXDA with adipic acid), di- (4-aminophenyl) methane, di- (4-amino-cyclohexyl) -methane, 2,2-di- (4-aminophenyl) -propane, 2,2-di- (4-aminocyclohexyl) -propane or 1,5-diamino-2- methylpentane.
  • Ultramid ® X17 from BASF SE, a 1: 1 molar ratio of MXDA with adipic acid
  • di- (4-aminophenyl) methane di- (4-amino-cyclohexyl) -methane
  • Preferred polyamides are Polyhexamethylenadipinklamid, Polyhexamethylensebacin- acid amide and polycaprolactam and copolyamides 6/66, in particular with a share of 5 to 95 wt .-% of caprolactam units (eg Ultramid ® C31 BASF SE).
  • polyamides are obtainable from ⁇ -aminoalkyl nitriles such as aminocapronitrile (PA 6) and adiponitrile with hexamethylenediamine (PA 66) by so-called direct polymerization in the presence of water, as for example in DE-A 10313681, EP-A 1 198491 and EP 922065.
  • PA 6 aminocapronitrile
  • PA 66 adiponitrile with hexamethylenediamine
  • polyamides may also be mentioned which are obtainable, for example, by condensation of 1,4-diaminobutane with adipic acid at elevated temperature (polyamide 4,6). Production processes for polyamides of this structure are described, for example, in EP-A 38 094, EP-A 38 582 and EP-A 39 524.
  • polyamides which are obtainable by copolymerization of two or more of the abovementioned monomers or mixtures of a plurality of polyamides are suitable, the mixing ratio being arbitrary. Particular preference is given to mixtures of polyamide 66 with other polyamides, in particular copolyamides 6/66.
  • the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
  • Further high-temperature-resistant polyamides are known from EP-A 19 94 075 (PA 6T / 6I / MXD6).
  • PA 46 tetramethylenediamine, adipic acid
  • PA 66 hexamethylenediamine, adipic acid
  • PA 610 hexamethylenediamine, sebacic acid
  • PA 612 hexamethylenediamine, decanedicarboxylic acid
  • PA 613 hexamethylenediamine, undecanedicarboxylic acid
  • PA 1212 1, 12-dodecanediamine, decanedicarboxylic acid
  • PA 1313 1, 13-diaminotridecane, undecanedicarboxylic acid
  • PA 6T hexamethylenediamine, terephthalic acid
  • PA 9T 1, 9-nonanediamine, terephthalic acid
  • PA MXD6 m-xylylenediamine, adipic acid
  • PA 61 hexamethylenediamine, isophthalic acid
  • PA 6-3-T trimethylhexamethylenediamine, terephthalic acid
  • PA 6 / 6T (see PA 6 and PA 6T)
  • PA 6/66 (see PA 6 and PA 66)
  • PA 6/12 see PA 6 and PA 12
  • PA 66/6/610 see PA 66, PA 6 and PA 610)
  • PA 6I / 6T see PA 61 and PA 6T
  • PA PA PACM 12 diaminodicyclohexylmethane, laurolactam
  • PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane
  • PA PDA-T phenylenediamine, terephthalic acid
  • R 1 is hydrogen or a C 1 -C 4 -alkyl group
  • R 2 is a Ci-C4-alkyl group or hydrogen
  • R 3 is a Ci-C4-alkyl group or hydrogen, into consideration.
  • Particularly preferred diamines are bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) -2,2-propane or bis (4-amino-3-methylcyclohexyl) -2 , 2-propane.
  • 1, 3 or 1,4-cyclohexanediamine or isophoronediamine may be mentioned as further diamines. It is also possible to use mixtures of the above polyamides.
  • thermoplastic molding compositions according to the invention contain from 0.5 to 20, preferably from 0.5 to 15, and in particular from 6 to 15,% by weight of a melamine compound.
  • the melam compound which is preferably suitable according to the invention is a condensation product preferably obtainable by thermal treatment of melamine compounds (formula I)
  • radicals R in (I) and (II) independently of one another denote hydrogen or an alkyl radical having 1 to 12 C atoms, preferably 1 to 4 C atoms.
  • Preferred preparations can be found in WO 96/16948 or EP-A 1252168.
  • Preferred flame retardant C) is elemental red phosphorus, in particular in combination with glass fiber-reinforced molding compositions, which can be used in untreated form.
  • preparations are particularly suitable in which the phosphorus on the surface with low molecular weight liquid substances such as silicone oil, paraffin oil or esters of phthalic acid or adipic acid or with polymeric or oligomeric compounds, eg. B. are coated with phenolic resins or aminoplasts and polyurethanes.
  • concentrates of red phosphorus, z. B. suitable in a polyamide or elastomers as a flame retardant.
  • polyolefin homo- and copolymers are useful as concentrate polymers.
  • the proportion of the concentrate polymer should not be more than 35% by weight, based on the weight of the components (A) and (B), in the molding compositions according to the invention.
  • Ci 30 to 90 wt .-%, preferably from 50 to 70 wt .-% of a polyamide.
  • the polyamide used for the batch can be different from A) or preferably equal to A), so that incompatibilities or melting point differences have no negative effect on the molding composition.
  • the average particle size (dso) of the phosphor particles distributed in the molding compositions is preferably in the range from 0.0001 to 0.5 mm; in particular from 0.001 to 0.2 mm.
  • the content of component C) in the molding compositions according to the invention is 0.1 to 60, preferably 0.5 to 40 and in particular 2 to 10 wt .-%, based on the sum of components A) to D).
  • the molding compositions according to the invention may contain from 0 to 60, in particular up to 50% by weight of further additives and processing aids.
  • fibrous or particulate fillers D1 carbon fibers, glass fibers, glass spheres, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar are mentioned, which in amounts of 1 to 50 wt .-%, in particular 1 to 40, preferably 10 to 40 wt .-% are used.
  • compositions contain
  • Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass or grinding glass in the commercial forms.
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.
  • Suitable silane compounds are those of the general formula
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of 0.01 to 2, preferably 0.025 to 1, 0 and in particular 0.05 to 0.5 wt .-% (based on D)) for surface coating.
  • long glass fibers as component D1) which can be used as roving.
  • the glass fibers used according to the invention as a roving have a diameter of 6 to 20 ⁇ m, preferably of 10 to 18 ⁇ m, the cross section of the glass fibers being round, oval or angular.
  • E-glass fibers are used according to the invention. But it can also all other types of glass fiber, such. A, C, D, M, S, R glass fibers or any mixtures thereof or mixtures with E glass fibers are used.
  • the L / D (length / diameter) ratio is 100 to 4000, in particular 350 to 2000 and very particularly 350 to 700.
  • acicular mineral fillers are also suitable.
  • the term "needle-shaped mineral fillers” is understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has an L / D (length: diameter ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1)
  • the mineral filler may optionally be pretreated with the silane compounds mentioned above, the pretreatment however, is not essential.
  • further fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called and additionally platelet or needle-shaped Nanoglal Istoff e preferably in amounts between 0.1 and 10%.
  • Boehmite, bentonite, montmorillonite, vermicullite, hectorite and laponite are preferably used for this purpose.
  • the platelet-shaped nanofillers according to the prior art are organically modified.
  • the addition of the platelet- or needle-shaped nanofillers to the nanocomposites according to the invention leads to a further increase in the mechanical strength.
  • Further customary additives D2) are, for example, in amounts of from 1 to 30, preferably from 2 to 20,% by weight of elastomeric polymers (often also referred to as impact modifiers, elastomers or rubbers).
  • compositions are:
  • elastomers In the following some preferred types of such elastomers are presented. Preferred types of such elastomers are the so-called ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM) rubbers.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers for example, conjugated dienes such as isoprene and butadiene, non-conjugated dienes with 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1, 4- dienes, hexa-1, 5-diene, 2,5-dimethylhexa-1, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadienes and alkenylnorbornenes such as 5-ethylidene 2-norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1 .0.2.6) -3,8- called decadiene or their mixtures.
  • conjugated dienes
  • the diene content of the EPDM rubbers is preferably 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
  • EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and its derivatives, e.g. Glycidyl (meth) acrylate, and called maleic anhydride.
  • Another group of preferred rubbers are copolymers of ethylene with acrylic acid and / or methacrylic acid and / or the esters of these acids.
  • the rubbers may still contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by addition of monomers containing dicarboxylic acid or epoxy groups of the general formulas I or II or III or IV to the monomer mixture
  • R 1 to R 9 are hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20, g is an integer from 0 to 10 and p is an integer from 0 to 5.
  • the radicals R 1 to R 9 preferably denote hydrogen, where m is 0 or 1 and g is 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl ether.
  • Preferred compounds of formulas I, II and IV are maleic acid, maleic anhydride and epoxy group-containing esters of acrylic acid and / or methacrylic acid, such as glycidyl acrylate, glycidyl methacrylate and the esters with tertiary alcohols, such as t-butyl acrylate. Although the latter have no free carboxyl groups, their behavior is close to the free acids and are therefore termed monomers with latent carboxyl groups.
  • the copolymers advantageously consist of 50 to 98% by weight of ethylene, 0.1 to 20% by weight of monomers containing epoxy groups and / or monomers containing methacrylic acid and / or acid anhydride groups, and the remaining amount
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • vinyl esters and vinyl ethers can also be used as comonomers.
  • the ethylene copolymers described above can be prepared by methods known per se, preferably by random copolymerization under high pressure and elevated temperature. Corresponding methods are generally known. Preferred elastomers are also emulsion polymers, their preparation e.g. at Blackley in the monograph "Emulsion Polymerization". The usable emulators and catalysts are known per se.
  • homogeneously constructed elastomers or else those with a shell structure can be used.
  • the shell-like structure is determined by the order of addition of the individual monomers; the morphology of the polymers is also influenced by this order of addition.
  • acrylates such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof may be mentioned as examples only.
  • These monomers can be mixed with other monomers such as styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates. th as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate are copolymerized.
  • the soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers may be the core, the outer shell or a middle shell (in elastomers with more than two-shell construction); in the case of multi-shell elastomers, it is also possible for a plurality of shells to consist of a rubber phase.
  • one or more hard components having glass transition temperatures of more than 20 ° C.
  • these are generally prepared by polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, acrylic esters and methacrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers.
  • acrylic esters and methacrylates such as methyl acrylate, ethyl acrylate and methyl methacrylate produced as main monomers.
  • smaller proportions of other comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, carbo xyl, latent carboxyl, amino or amide groups and functional groups obtained by concomitant use of monomers of the general formula
  • R 10 is hydrogen or a C 1 - to C 4 -alkyl group
  • R 11 is hydrogen, a C 1 - to C 5 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a C 1 - to C 10 -alkyl, a C 1 - to C 12 -aryl group or -OR 13 is a C 1 - to C 8 -alkyl or C 1 - to C 12 -aryl group which is optionally substituted by O- or N-containing groups may be a chemical bond, a C 1 to C 10 alkylene or C 6 to C 12 arylene group
  • Z is a C 1 -C 10 -alkylene or C 6 -C 12 -arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide methacrylamide and substituted esters of acrylic acid or methacrylic acid, such as (Nt-butylamino) -ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) -methyl acrylate and ( N, N-diethylamino) ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • monomers acting as crosslinkers are buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and also the compounds described in EP-A 50 265.
  • graft-linking monomers can also be used, i. Monomers having two or more polymerizable double bonds, which react at different rates in the polymerization. Preferably, those compounds are used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) is e.g. polymerized much slower (polymerize). The different polymerization rates bring a certain proportion of unsaturated double bonds in the rubber with it. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the grafting monomers to form chemical bonds, ie. the grafted phase is at least partially linked via chemical bonds to the graft base.
  • graft-crosslinking monomers examples include allyl-containing monomers, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoallyl compounds of these dicarboxylic acids.
  • allyl-containing monomers in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate or the corresponding monoally
  • the proportion of these crosslinking monomers in the impact-modifying polymer is up to 5% by weight, preferably not more than 3% by weight, based on the impact-modifying polymer.
  • some preferred emulsion polymers are listed.
  • graft polymers having a core and at least one outer shell which have the following structure: Type monomers for the core monomers for the shell
  • III such as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate, buta-1, 3-diene, isoprene, ethylhexyl acrylate
  • V styrene, acrylonitrile, methyl methacrylate or first shell of monomers as under I
  • graft polymers having a multi-shell structure instead of graft polymers having a multi-shell structure, homogeneous, i. single-shell elastomers of buta-1,3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be prepared by concomitant use of crosslinking monomers or monomers having reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers having an inner core of n-butyl acrylate or butadiene-based and an outer shell of the above copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the described elastomers may also be prepared by other conventional methods, e.g. by suspension polymerization.
  • Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290, are likewise preferred. It is also possible to use mixtures of such rubbers.
  • the molding compositions according to the invention may contain 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.
  • a lubricant Preference is given to Al, alkali metal, alkaline earth metal salts or esters or amides of fatty acids having 10 to 44 carbon atoms, preferably having 12 to 44 carbon atoms.
  • the metal ions are preferably alkaline earth and Al, with Ca or Mg being particularly preferred.
  • Preferred metal salts are Ca-stearate and Ca-montanate as well as Al-stearate.
  • the carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).
  • the aliphatic alcohols can be 1 - to 4-valent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, ethylenediamine and hexamethylenediamine being particularly preferred. Accordingly, preferred esters or amides are glycerin distearate, glycerol tristearate, ethylenediamine distearate, glycerin monopalmitate, glycerol trilaurate, glycerin monobehenate and pentaerythritol tetrastearate.
  • the molding compositions of the invention 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a Cu stabilizer, preferably a Cu (I) halide, in particular Mixture with an alkali metal halide, preferably KJ, in particular in the ratio 1: 4, or contain a sterically hindered phenol or mixtures thereof.
  • Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. These are contained in amounts of 5 to 500 ppm of copper, preferably 10 to 250 ppm, based on polyamide.
  • the advantageous properties are obtained in particular when the copper is present in molecular distribution in the polyamide.
  • This is achieved by adding to the molding compound a concentrate containing polyamide, a salt of monovalent copper and an alkali halide in the form of a solid, homogeneous solution.
  • a typical concentrate consists eg of 79 to 95% by weight.
  • the concentration of the solid homogeneous solution of copper is preferably between 0.3 and 3, in particular between 0.5 and 2 wt .-%, based on the total weight of the solution and the molar ratio of copper (I) iodide to potassium iodide is between 1 and 1 1, 5, preferably between 1 and 5.
  • Suitable polyamides for the concentrate are homopolyamides and copolyamides, in particular polyamide 6 and polyamide 6.6.
  • Suitable hindered phenols D3) are in principle all compounds having a phenolic structure which have at least one sterically demanding group on the phenolic ring.
  • R 1 and R 2 are an alkyl group, a substituted alkyl group or a substituted triazole group, wherein the radicals R 1 and R 2 may be the same or different and R 3 is an alkyl group, a substituted alkyl group, an alkoxy group or a substituted amino group.
  • Antioxidants of the type mentioned are described, for example, in DE-A 27 02 661 (US Pat. No. 4,360,617).
  • Another group of preferred sterically hindered phenols are derived from substituted benzenecarboxylic acids, especially substituted benzenepropionic acids.
  • Particularly preferred compounds of this class are compounds of the formula
  • R 4 , R 5 , R 7 and R 8 independently of one another are C 1 -C 8 -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding group) and R 6 is a bivalent aliphatic radical having 1 to 10 C atoms means that in the main chain can also have CO bonds.
  • R 4 , R 5 , R 7 and R 8 independently of one another are C 1 -C 8 -alkyl groups which in turn may be substituted (at least one of which is a sterically demanding group) and R 6 is a bivalent aliphatic radical having 1 to 10 C atoms means that in the main chain can also have CO bonds.
  • Preferred compounds corresponding to these formulas are
  • the antioxidants D3) which can be used individually or as mixtures, are in an amount of 0.05 to 3 wt .-%, preferably from 0.1 to 1, 5 wt .-%, in particular 0.1 to 1 Wt .-%, based on the total weight of the molding compositions A) to D).
  • sterically hindered phenols having no more than one sterically hindered group ortho to the phenolic hydroxy group have been found to be particularly advantageous; especially when assessing color stability when stored in diffused light for extended periods of time.
  • the molding compositions according to the invention may contain 0.05 to 5, preferably 0.1 to 2 and in particular 0.25 to 1, 5 wt .-% of a nigrosine.
  • Nigrosines are generally understood to mean a group of black or gray indulene-related phenazine dyes (azine dyes) in various embodiments (water-soluble, fat-soluble, gas-soluble) used in wool dyeing and printing, in black dyeing of silks, for dyeing of leather, shoe creams, varnishes, plastics, stoving lacquers, inks and the like, as well as being used as microscopy dyes.
  • the nigrosine is technically obtained by heating nitrobenzene, aniline and aniline with anhydrous metal. Iron and FeC.
  • Component D3) can be used as the free base or else as the salt (for example hydrochloride).
  • nigrosines can be found, for example, in the electronic lexicon Rompp Online, Version 2.8, Thieme-Verlag Stuttgart, 2006, keyword "nigrosine".
  • thermoplastic molding compositions according to the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation inhibitors and heat stabilizers are sterically hindered phenols and / or phosphites and amines (eg TAD), hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof and iron powder (from iron pentacarbonyl) in concentrations up to 1 Wt .-%, based on the weight of the thermoplastic molding compositions called.
  • TAD sterically hindered phenols and / or phosphites and amines
  • hydroquinones such as diphenylamines
  • various substituted representatives of these groups and mixtures thereof iron powder (from iron pentacarbonyl) in concentrations up to 1 Wt .-%, based on the weight of the thermoplastic molding compositions called.
  • iron powder from iron pentacarbonyl
  • UV stabilizers which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, sal
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones as colorants.
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as anthraquinones
  • nucleating agents sodium phenylphosphinate, alumina, silica and preferably talc may be used.
  • the novel thermoplastic molding compositions can be prepared by processes known per se, in which the starting components are mixed in customary mixing devices, such as screw extruders, Brabender mills or Banbury mills, and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually between 230 and 320 ° C.
  • the components B) and optionally C) can be mixed with a prepolymer, formulated and granulated.
  • the resulting granules are then condensed in solid phase under inert gas continuously or discontinuously at a temperature below the melting point of component A) to the desired viscosity.
  • thermoplastic molding compositions according to the invention are characterized by a good coloration and flame retardancy, in particular by good glow wire test, with at the same time good mechanical properties.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • Cylinder head covers are suitable for the production of fibers, films and moldings of any kind.
  • engine covers intake pipes, intercooler caps, connectors, gears, fan wheels, cooling water boxes.
  • FPC flexible printed circuit
  • FFC flexible integrated circuit connectors
  • high-speed connectors terminal blocks, connectors, connectors, harness components, circuit carriers, circuit carrier components, three-dimensional injection-molded circuit carriers, electrical connectors, mechatronic components are manufactured.
  • dashboards In the car interior, there is use for dashboards, steering column switches, seat parts, headrests, center consoles, transmission components and door modules, in the car exterior for door handles, exterior mirror components, windshield wiper components, windscreen wiper housings, grilles, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds (In particular intake manifold), windscreen wipers and body exterior parts possible.
  • intake manifolds In particular intake manifold
  • windscreen wipers In particular intake manifold
  • body exterior parts possible.
  • Component A Component A:
  • Melamine polyphosphate Melamine polyphosphate (Melapur® 200 from BASF SE)
  • the molding compositions were prepared on a ZSK 18 at a throughput of 30 kg / h and about 290 ° C flat temperature profile.
  • the fire protection properties were determined according to UL94 on 0.8 mm thick bars. Storage conditions: 2 days, 23 ° C. The total afterburning time was determined on 5 samples under standard conditions.
  • compositions of the molding compositions and the results of the measurements are shown in the tables.
  • All molding compositions contained 1, 54 wt .-% in total lubricant (Caiciumstearat) and stabilizers (zinc oxide, Irganox® 1098 BASF).

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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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne des matières à mouler thermoplastiques, contenant : A) de 10 à 99,4 % en poids d'au moins un polyamide thermoplastique ; B) de 0,5 à 20 % en poids d'un composé mélaminé ; C) de 0,1 à 60 % en poids de phosphore rouge ; D) de 0 à 60 % en poids d'autres additifs, la somme des pourcentages en poids A) à D) étant égale à 100 %.
PCT/EP2012/057576 2011-04-28 2012-04-25 Matières à mouler ignifugées WO2012146624A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR112013027454A BR112013027454A2 (pt) 2011-04-28 2012-04-25 composição de moldagem termoplástica, uso das composições de moldagem termoplástica, e, fibra, folha ou moldagem
JP2014506849A JP2014517093A (ja) 2011-04-28 2012-04-25 難燃性成形材料
EP12716451.5A EP2702102A1 (fr) 2011-04-28 2012-04-25 Matières à mouler ignifugées
CN201280020075.5A CN103492488A (zh) 2011-04-28 2012-04-25 阻燃性模塑组合物

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EP11164108 2011-04-28
EP11164108.0 2011-04-28

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WO2012146624A1 true WO2012146624A1 (fr) 2012-11-01

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JP (1) JP2014517093A (fr)
CN (1) CN103492488A (fr)
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WO (1) WO2012146624A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8987357B2 (en) 2011-05-27 2015-03-24 Basf Se Thermoplastic molding composition

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CN111138850B (zh) * 2019-12-12 2021-08-13 金发科技股份有限公司 一种聚酰胺复合材料及其制备方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8987357B2 (en) 2011-05-27 2015-03-24 Basf Se Thermoplastic molding composition

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BR112013027454A2 (pt) 2019-09-24
JP2014517093A (ja) 2014-07-17
EP2702102A1 (fr) 2014-03-05
CN103492488A (zh) 2014-01-01

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