WO2008132111A1 - Matières thermoplastiques à mouler ignifugées - Google Patents

Matières thermoplastiques à mouler ignifugées Download PDF

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Publication number
WO2008132111A1
WO2008132111A1 PCT/EP2008/054920 EP2008054920W WO2008132111A1 WO 2008132111 A1 WO2008132111 A1 WO 2008132111A1 EP 2008054920 W EP2008054920 W EP 2008054920W WO 2008132111 A1 WO2008132111 A1 WO 2008132111A1
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molding compositions
acid
weight
thermoplastic molding
thermoplastic
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PCT/EP2008/054920
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German (de)
English (en)
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Claudia Mettlach
Alexander SCHÄFER
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Basf Se
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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
    • C08K5/34928—Salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—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'

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • thermoplastic polyamide or polyester A) 10 to 98 wt .-% of a thermoplastic polyamide or polyester
  • substituents have the following meanings: X, Y, Z independently of one another are hydrogen or halogen, R 1 , R 2, independently of one another, are hydrogen or methyl,
  • R 3 OH, or an O-alkyl group with a polyhydric alcohol having at least 3 hydroxyl groups or an optionally substituted triazine ring.
  • the invention relates to the use of the thermoplastic molding compositions for the production of moldings of any kind and the moldings obtainable in this case of any kind.
  • DOP 9,10-dihydro-9-oxa-10-phospha-phenanthren-10-oxide
  • DOP derivatives which are suitable for flame retardancy are known from EP-A 10 90 922 and US 4,280,951.
  • DOP derivatives for polyamide / polyester and (styrene) foams are known from Proceedings of the Conference on Recent Advances in Flame Retardancy of Polymeric Material (2005), 16, 83 to 92 and DE-A 10 20004 044 380. It will Synergists proposed for better flame retardancy, as at the high processing temperatures, especially glass fiber-containing polyamides, DOP derivatives decompose massively.
  • thermoplastic polymers The effect of the flame retardants used in thermoplastic polymers is often unpredictable with polymer foams due to the different fire behavior and different fire tests.
  • Object of the present invention was therefore to find a flame retardant system for polyamide / polyester molding compositions, which has good flame retardancy and good glow wire resistance, the flowability / processability is to be maintained.
  • the molding compositions according to the invention contain from 10 to 98, preferably from 30 to 98, and in particular from 40 to 96,% by weight of at least one thermoplastic polyester.
  • polyesters A) based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.
  • a first group of preferred polyesters are polyalkylene terephthalates, in particular those having 2 to 10 carbon atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid.
  • the aromatic ring may also be substituted, e.g. by halogen, such as chlorine and bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, isopropyl or n-propyl and n, i and t-butyl groups.
  • polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
  • aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof.
  • polyesters (A) are polyalkylene terephthalates, which differ from
  • Derive alkanediols having 2 to 6 carbon atoms to name.
  • polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof Preference is furthermore given to PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
  • the viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (wt. 1 at 25 ° C.) according to ISO 1628.
  • polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg of polyester.
  • Such polyesters can be prepared, for example, by the process of DE-A 44 01 055.
  • the carboxyl end group content is usually determined by titration methods (e.g., potentiometry).
  • Particularly preferred molding compositions contain as component A) a mixture of polyesters which are different from PBT, such as, for example, polyethylene terephthalate (PET).
  • PBT polyethylene terephthalate
  • the proportion e.g. of the polyethylene terephthalate is preferably in the mixture up to 50, in particular 10 to 35 wt .-%, based on 100 wt .-% A).
  • PET recyclates also termed scrap PET
  • PBT polyalkylene terephthalates
  • Post Industrial Recyclate this refers to production waste during polycondensation or during processing, eg sprues during injection molding, start-up goods in injection molding or extrusion or edge sections of extruded sheets or foils.
  • Post Consumer Recyclate These are plastic items that are collected and processed after use by the end user. By far the dominating items in terms of volume are blow-molded PET bottles for mineral water, soft drinks and juices.
  • Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.
  • the maximum edge length should be 10 mm, preferably less than 8 mm.
  • the residual moisture content after drying is preferably ⁇ 0.2%, in particular ⁇ 0.05%.
  • Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to using mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% of terephthalic acid with 20% of isophthalic acid to approximately equivalent mixtures of these two acids.
  • the aromatic dihydroxy compounds preferably have the general formula
  • Z represents an alkylene or cycloalkylene group having up to 8 C atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m the value 0 to 2 has.
  • the compounds may also carry C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents on the phenylene groups.
  • these compounds are, for example
  • Dihydroxydiphenyl di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di- (hydroxyphenyl) sulfoxide, ⁇ , ⁇ '-di - (hydroxyphenyl) -dialkylbenzol,
  • polyester block copolymers such as copolyether esters can also be used.
  • Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014.
  • corresponding products are available, eg Hytrel® (DuPont).
  • As a polyester to be understood according to the invention also halogen-free polycarbonates. Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula
  • Q is a single bond, a C 1 to C 5 alkylene, a C 2 to C 3 alkylidene, a C 3 to C 6 cycloalkylidene group, a C 6 to C 12 arylene group, and -O-, -S- or -SO 2 - and m is an integer from 0 to 2.
  • the diphenols may also have substituents on the phenylene radicals, such as C 1 - to C 6 -alkyl or C 1 - to C 6 -alkoxy.
  • Preferred diphenols of the formula are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1 bis (4-hydroxyphenyl) -cyclohexane.
  • Particularly preferred are 2,2-bis (4-hydroxyphenyl) propane and 1, 1-bis (4-hydroxyphenyl) cyclohexane, and 1, 1-bis (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane.
  • both homopolycarbonates and copolycarbonates are suitable as component A; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates may be branched in a known manner, preferably by the incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those having three or more than three phenolic compounds OH groups.
  • the relative viscosities ⁇ rei of 1, 10 to 1, 50, in particular from 1, 25 to 1, 40 have. This corresponds to average molecular weights M w (weight average) of from 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.
  • the diphenols of the general formula are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), where the particular molecular weight to be set is achieved in a known manner by an appropriate amount of known chain terminators.
  • phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process)
  • Suitable chain terminators are, for example, phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-A 35 06 472, such as p-nonylphenol, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- (3, 5-dimethylheptyl) -phenol.
  • alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents according to DE-
  • Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of subordinate ppm amounts of saponifiable chlorine resulting, for example, from the preparation of the polycarbonates with phosgene Phase interface method, not to be regarded as halogen-containing in the context of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.
  • suitable components A) may be mentioned amorphous polyester carbonates, wherein phosgene was replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units in the preparation.
  • bisphenol A can be replaced by bisphenol TMC.
  • polycarbonates are available under the trademark APEC HT® from Bayer.
  • the molding compositions according to the invention contain 10 to 98, preferably 20 to 98 and in particular 40 to 96 wt .-% of at least one polyamide.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 70 to 350, preferably 70 to 170 ml / g, determined in a 0.5 wt .-% solution in 96 wt .-% sulfuric acid at 25 ° C according to ISO 307th
  • polyamides which are derived from lactams having 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurolactam, and also polyamides which are obtained by reacting dicarboxylic acids with diamines.
  • 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 are mentioned as acids.
  • Suitable diamines are in particular alkanediamines having 6 to 12, in particular 6 to 8 carbon atoms and m-xylylenediamine, 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-methyl-pentane.
  • Preferred polyamides are polyhexamethylene adipamide, polyhexamethylene sebacamide and polycaprolactam and also copolyamides 6/66, in particular with a content of 5 to 95% by weight of caprolactam units.
  • polyamides are obtainable from ⁇ -aminoalkyl nitriles such as, for example, 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 described.
  • ⁇ -aminoalkyl nitriles such as, for example, 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 described.
  • polyamides which are e.g. are obtainable by condensation of 1, 4-diaminobutane with adipic acid at elevated temperature (polyamide 4.6). Manufacturing processes for polyamides of this structure are known e.g. in EP-A 38 094, EP-A 38 582 and EP-A 39 524 described.
  • 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.
  • the triamine content is less than 0.5, preferably less than 0.3 wt .-% (see EP-A 299 444).
  • PA 1 1 1 1-aminoundecanoic acid
  • 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 MXD6 m-xylylenediamine, adipic 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 6I and PA 6T)
  • PA PACM 12 diaminodicyclohexylmethane, laurinlactam
  • PA 6I / 6T / PACM such as PA 6I / 6T + diaminodicyclohexylmethane
  • PA 12 / MACMI laurolactam dimethyldiaminodicyclohexylmethane
  • PA 12 / MACMT laurolactam dimethyldiaminodicyclohexylmethane
  • 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 are mentioned as further diamines.
  • thermoplastic molding compositions according to the invention contain from 1 to 30, preferably from 1 to 20, and in particular from 1 to 10,% by weight of melamine cyanurate.
  • the melamine cyanurate suitable according to the invention (component B) is a reaction product of preferably equimolar amounts of melamine (formula II) and cyanoic acid or isocyanuric acid (formulas IIa and IIb)
  • the molding compositions according to the invention contain 1 to 30, preferably 1 to 20 and in particular 5 to 20 wt .-% of a phosphorus compound of the general formula I.
  • substituents have the following meanings: X, Y, Z independently of one another are hydrogen or halogen, R 1 , R 2, independently of one another, are hydrogen or methyl,
  • R 3 OH, or an O-alkyl group with a polyhydric alcohol having at least 3 hydroxyl groups or an optionally substituted triazine ring.
  • radical R 3 in the general formula I for C an O-alkyl group with a polyhydric alcohol selected from the group of glycerol, polyglycerol, Trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, mannitol or sorbitol or their mixture or a triazine ring.
  • a polyhydric alcohol selected from the group of glycerol, polyglycerol, Trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, tetrapentaerythritol, mannitol or sorbitol or their mixture or a triazine ring.
  • Component C) preferably has a phosphorus content of from 5 to 11, preferably from 6 to 10.7% by weight, based on C).
  • the softening temperature is preferably from 55 to 155 0 C (by DSC). Particular preference is given as component C)
  • the molding compositions of the invention may contain 0 to 60, preferably up to 40 wt .-% of other additives.
  • the molding compositions according to the invention may contain 0 to 3, preferably 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-% of a lubricant.
  • 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. It is also possible to use mixtures of different salts, the mixing ratio being arbitrary.
  • 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 monohydric to trihydric. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • preferred esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • the molding compositions according to the invention may comprise heat stabilizers or antioxidants or mixtures thereof selected from the group consisting of copper compounds, sterically hindered phenols, sterically hindered aliphatic amines and / or aromatic amines.
  • Copper compounds are in the novel PA molding compositions to 0.05 to 3, preferably 0.1 to 1, 5 and in particular 0.1 to 1 wt .-%, preferably as Cu (l) halide, in particular in a mixture with an alkali halide, preferably KJ, in particular in the ratio 1: 4, or a sterically hindered phenol or an amine stabilizer or mixtures thereof.
  • Suitable salts of monovalent copper are preferably copper (I) acetate, copper (I) chloride, bromide and iodide. They are contained in amounts of 5 to 500 ppm 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 con- For example, concentrate consists of 79 to 95 wt .-% polyamide and 21 to 5 wt .-% of a mixture of copper iodide or bromide and potassium iodide.
  • 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 11, 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 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 d-Ce-alkyl groups which in turn may be substituted (at least one of which is a sterically demanding full group) and R 6 is a divalent aliphatic radical having 1 to 10 carbon atoms, which may also have CO bonds in the main chain.
  • the phenolic antioxidants which may be used singly or as mixtures are in an amount of 0.05 to 3% by weight, preferably 0.1 to 1.5% by weight, more preferably 0.1 to 1% by weight .-%, based on the total weight of the molding compositions A) to D) included.
  • 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.
  • fibrous or particulate fillers D are carbon fibers, glass fibers, glass beads, amorphous silica, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts up to 40 wt .-%, in particular 1 to 15 wt .-% are used.
  • 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 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
  • X is NM -, CH 2 -CH-, HO-,
  • m is an integer from 1 to 5, preferably 1 to 2
  • k is an integer from 1 to 3, preferably 1
  • 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 the fibrous fillers) for surface coating. Also suitable are acicular mineral fillers.
  • needle-shaped mineral fillers are understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has a UD (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
  • the mineral filler may optionally be pretreated with the aforementioned silane compounds; however, pretreatment is not absolutely necessary.
  • fillers are kaolin, calcined kaolin, wollastonite, talc and chalk called as well as platelet or needle-shaped nanofillers 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.
  • talc which is a hydrated magnesium silicate of the composition Mg3 [(OH) 2 / Si4 ⁇ io] or 3MgO4SiO2 H2O.
  • Mg3 [(OH) 2 / Si4 ⁇ io] or 3MgO4SiO2 H2O.
  • Mn, Ti, Cr, Ni, Na and K may be present, wherein the OH group may be partially replaced by fluoride.
  • talc the particle size of which is 99.5% ⁇ 20 ⁇ m.
  • the particle size distribution is usually determined by sedimentation analysis and is preferably:
  • Such products are commercially available as Micro-Tale IT. Extra (Omya) available.
  • Examples of impact modifiers are rubbers which may have functional groups. It is also possible to use mixtures of two or more different impact-modifying rubbers.
  • Rubbers which enhance the toughness of the molding compositions generally comprise an elastomeric portion which can have a glass transition temperature of less than -10 0 C, preferably less than -30 0 C, and at least they contain a functional group reactive with the polyamic , Suitable functional groups are, for example, carboxylic acid, carboxylic acid anhydride, carboxylic ester, carboxamide, carboxylic imide, amino, hydroxyl, epoxide, urethane or oxazoline groups, preferably carboxylic anhydride groups.
  • Preferred functionalized rubbers include functionalized polyolefin rubbers which are composed of the following components:
  • Ci-Ci2-alkyl ester of acrylic acid or methacrylic acid or mixtures of such esters 4. 0 to 40 wt .-% of an ethylenically unsaturated C2-C2o mono- or dicarboxylic acid or a functional derivative such an acid,
  • alpha-olefins there can be mentioned ethylene, propylene, 1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene, 2-methylpropylene, 3-methyl-1-butylene and 3-ethyl-1. butylene, with ethylene and propylene being preferred.
  • Suitable diene monomers are conjugated dienes having 4 to 8 C atoms, such as isoprene and butadiene, non-conjugated dienes having 5 to 25 C atoms, such as penta-1,4-diene, hexa-1,4-diene , Hexa-1, 5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene, as well as alkenylnorbornene such as 5-ethylidene-2 norbornene, 5-butylidene-2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes, such as 3-methyltricyclo (5.2.1.0 26 ) -3,8-decadiene, or
  • the diene content is preferably 0.5 to 50, in particular 2 to 20 and particularly preferably 3 to 15 wt .-%, based on the total weight of the olefin polymer.
  • suitable esters are methyl, ethyl, propyl, n-butyl, i-butyl and 2-ethyl hexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, methyl, ethyl, propyl, n-butyl and 2-ethylhexyl acrylate or methacrylate are particularly preferred.
  • acid-functional and / or latent acid-functional monomers of ethylenically unsaturated monocarboxylic or dicarboxylic acids may also be present in the olefin polymers.
  • ethylenically unsaturated mono- or dicarboxylic acids are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and dicarboxylic acids, such as maleic acid and fumaric acid, or derivatives of these acids and their monoesters.
  • Latent acid-functional monomers are understood as meaning those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions.
  • Examples of these are anhydrides of dicarboxylic acids having 2 to 20 carbon atoms, in particular maleic anhydride and tertiary Ci-Ci2-alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.
  • olefin polymers from 50 to 98.9, in particular 60 to 94.85 wt .-% of ethylene, and 1 to 50, in particular 5 to 40 wt .-% of an ester of acrylic or methacrylic acid 0.1 to 20.0 , in particular 0.15 to 15 wt .-% glycidyl acrylate and / or glycidyl methacrylate, acrylic acid and / or maleic anhydride.
  • Particularly suitable functionalized rubbers are ethylene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl acrylate and ethylene-methyl methacrylate-glycidyl acrylate polymers.
  • the preparation of the polymers described above can be carried out by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.
  • the melt index of these copolymers is generally in the range of 1 to 80 g / 10 min (measured at 190 0 C and 2.16 kg load).
  • Suitable rubbers are core-shell graft rubbers. These are graft rubbers made in emulsion, which consist of at least one hard and one soft component.
  • a hard constituent is usually understood to mean a polymer having a glass transition. a polymer having a glass transition temperature of at most 0 0 C.
  • These products have a structure of a core and at least one shell, wherein the structure results by the order of addition of monomer.
  • the soft components are generally derived from butadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanes and optionally further comonomers.
  • Suitable siloxane cores can be prepared, for example, starting from cyclic oligomeric octamethyltetrasiloxane or tetravinyltetramethyltetrasiloxane. These can be reacted, for example, with gamma-mercaptopropylmethyldimethoxysilane in a ring-opening cationic polymerization, preferably in the presence of sulfonic acids, to form the soft siloxane chains.
  • the siloxanes may also be crosslinked by, for example, carrying out the polymerization reaction in the presence of silanes having hydrolyzable groups such as halogen or alkoxy groups such as tetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane.
  • Suitable comonomers here are, for example, styrene, acrylonitrile and crosslinking or graft-active monomers having more than one polymerizable double bond, such as diallyl phthalate, divinylbenzene, butanediol diacrylate or triallyl (iso) cyanurate.
  • the hard constituents are generally derived from styrene, alpha-methylstyrene and their copolymers, in which case comonomers are preferably acrylonitrile, methacrylonitrile and methyl methacrylate.
  • Preferred core-shell graft rubbers include a soft core and a hard shell or hard core, a first soft shell and at least one other hard shell.
  • the incorporation of functional groups such as carbonyl, carboxylic acid, acid anhydride, acid amide, acid imide, carboxylic acid ester, amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl groups , is preferably carried out by the addition of suitably functionalized monomers in the polymerization of the last shell.
  • Suitable functionalized monomers are, for example, maleic acid, maleic anhydride, mono- or diesters of maleic acid, tert-butyl (meth) acrylate, acrylic acid, glycidyl (meth) acrylate and vinyloxazoline.
  • the proportion of monomers having functional groups is generally from 0.1 to 25 wt .-%, preferably 0.25 to 15 wt .-%, based on the total weight of the core-shell graft rubber.
  • the weight ratio of soft to hard components is generally 1: 9 to 9: 1, preferably 3: 7 to 8: 2.
  • polyester elastomers include segmented copolyesters. ether esters understood, the long-chain segments, which are usually of poly (alkylene) ether glycols and short-chain segments derived from low molecular weight diols and dicarboxylic acids. Such products are known per se and described in the literature, for example in US Pat. No. 3,651,014. Also commercially available are corresponding products under the names Hytrel TM (Du Pont), Arnitel TM (Akzo) and Pelprene TM (Toyobo Co. Ltd.).
  • thermoplastic molding compositions according to the invention can contain conventional processing aids such as stabilizers, oxidation retardants, further agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc.
  • processing aids such as stabilizers, oxidation retardants, further agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, flame retardants, etc.
  • antioxidants and heat stabilizers include phosphites and further amines (eg TAD), hydroquinones, various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
  • TAD phosphites and further amines
  • hydroquinones various substituted representatives of these groups and mixtures thereof in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions.
  • UV stabilizers which are generally used in amounts of up to 2% by weight, based on the molding composition, of various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black and / or graphite, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants.
  • sodium phenylphosphinate, alumina, silica and preferably talc may be used as nucleating agents.
  • 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 230 to 320 0 C.
  • the components B) to C) and optionally D) can be mixed with a prepolymer, formulated and granulated.
  • the granules obtained 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.
  • the emulsion polymer B) is incorporated as a solids-containing dispersion in the melt of A).
  • thermoplastic molding compositions according to the invention are distinguished by good glow-wire resistance and flameproofing properties as well as good processability / flowability.
  • Component B is a compound having Component B:
  • the components A) to C) were made up to a twin-screw extruder at 260 0 C (component A1) and at 280 0 C (component A2) and (at 260 ° C A1), and 270 0 C (A2) melt temperature to give test specimens injected.
  • compositions of the molding compositions and the results of the measurements are shown in the table.

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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

La présente invention concerne des matières thermoplastiques à mouler qui contiennent A) de 10 à 98% en poids d'un polyamide ou d'un polyester thermoplastique, B) de 1 à 30% en poids d'un cyanurate de méthyle, C) de 1 à 30% en poids d'un composé phosphoré de formule générale (I) dans laquelle les substituants ont les significations suivantes : X, Y, Z représentent indépendamment hydrogène ou halogène, R1, R2 représentent indépendamment hydrogène ou méthyle, R3 représente OH ou un groupe O-alkyle présentant un alcool polyvalent avec au moins 3 groupes hydroxyle ou un cycle triazine éventuellement substitué, D) de 0 à 60% en poids d'autres additifs, la somme des pourcentages A) à D) s'élevant à 100%.
PCT/EP2008/054920 2007-04-26 2008-04-23 Matières thermoplastiques à mouler ignifugées WO2008132111A1 (fr)

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Cited By (18)

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WO2012080403A1 (fr) 2010-12-16 2012-06-21 Basf Se Polyamides résistants au fil incandescent
US8575295B2 (en) 2010-12-16 2013-11-05 Basf Se Glow-wire resistant polyamides
CN106800574A (zh) * 2017-01-16 2017-06-06 海泰纺织（苏州）有限公司 一种端羧基有机含磷‑氮‑硫酯化物及其制备方法和由其制得的阻燃涤纶织物
CN106810578A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端巯基有机含磷‑氮‑硫酯化物及其制备方法和由其制得的阻燃聚酯纤维poy丝
CN106810680A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端羟基有机含磷‑氮‑硫酯化物及其制备方法和由其制得的阻燃棉织物
CN106810681A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端羟基有机含磷酯化物及其制备方法和由其制得的阻燃涤纶织物
CN106810579A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端羟基有机含磷‑氮酯化物及其制备方法和由其制得的阻燃聚酯纤维fdy丝
CN106831877A (zh) * 2017-01-16 2017-06-13 海泰纺织（苏州）有限公司 一种端基为酸性基团的有机含磷酯化物及其制备方法和由其制得的阻燃聚酰胺6织物
CN106835340A (zh) * 2017-01-16 2017-06-13 海泰纺织（苏州）有限公司 一种端巯基有机含磷‑硫酯化物及其制备方法和由其制得的阻燃聚酯纤维hoy丝
CN106831552A (zh) * 2017-01-16 2017-06-13 东华大学 一种端基为巯基的有机含氮‑硫酯化物及其制备方法
CN106866740A (zh) * 2017-01-16 2017-06-20 东华大学 一种酯化物及其制备方法
CN106866517A (zh) * 2017-01-16 2017-06-20 东华大学 一种端基为羧酸基的有机含氮‑硫酯化物及其制备方法
CN106866734A (zh) * 2017-01-16 2017-06-20 东华大学 一种端基为酸性基团的有机含磷‑氮酯化物及其制备方法
CN106866516A (zh) * 2017-01-16 2017-06-20 东华大学 一种端基为羧酸基的有机含氮酯化物及其制备方法
CN107074892A (zh) * 2014-05-30 2017-08-18 纳幕尔杜邦公司 阻燃剂、制备方法及其热塑性组合物
US9856365B2 (en) 2011-08-31 2018-01-02 Radici Plastics Usa, Inc. Compositions of polyhydric alcohols and polyamides
DE102018222396A1 (de) 2018-12-20 2020-06-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Phosphorhaltige Polyacrylamide und deren Verwendung als Flammschutzmittel
WO2021254993A1 (fr) 2020-06-17 2021-12-23 Renolit Se Acrylate résistant à la flamme

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Cited By (24)

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Publication number Priority date Publication date Assignee Title
WO2012080403A1 (fr) 2010-12-16 2012-06-21 Basf Se Polyamides résistants au fil incandescent
CN103328558A (zh) * 2010-12-16 2013-09-25 巴斯夫欧洲公司 耐灼热丝的聚酰胺
US8575295B2 (en) 2010-12-16 2013-11-05 Basf Se Glow-wire resistant polyamides
US9856365B2 (en) 2011-08-31 2018-01-02 Radici Plastics Usa, Inc. Compositions of polyhydric alcohols and polyamides
CN107074892A (zh) * 2014-05-30 2017-08-18 纳幕尔杜邦公司 阻燃剂、制备方法及其热塑性组合物
CN106866517A (zh) * 2017-01-16 2017-06-20 东华大学 一种端基为羧酸基的有机含氮‑硫酯化物及其制备方法
CN106866516A (zh) * 2017-01-16 2017-06-20 东华大学 一种端基为羧酸基的有机含氮酯化物及其制备方法
CN106810579A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端羟基有机含磷‑氮酯化物及其制备方法和由其制得的阻燃聚酯纤维fdy丝
CN106831877A (zh) * 2017-01-16 2017-06-13 海泰纺织（苏州）有限公司 一种端基为酸性基团的有机含磷酯化物及其制备方法和由其制得的阻燃聚酰胺6织物
CN106835340A (zh) * 2017-01-16 2017-06-13 海泰纺织（苏州）有限公司 一种端巯基有机含磷‑硫酯化物及其制备方法和由其制得的阻燃聚酯纤维hoy丝
CN106831552A (zh) * 2017-01-16 2017-06-13 东华大学 一种端基为巯基的有机含氮‑硫酯化物及其制备方法
CN106866740A (zh) * 2017-01-16 2017-06-20 东华大学 一种酯化物及其制备方法
CN106810680A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端羟基有机含磷‑氮‑硫酯化物及其制备方法和由其制得的阻燃棉织物
CN106866734A (zh) * 2017-01-16 2017-06-20 东华大学 一种端基为酸性基团的有机含磷‑氮酯化物及其制备方法
CN106810681A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端羟基有机含磷酯化物及其制备方法和由其制得的阻燃涤纶织物
CN106810578A (zh) * 2017-01-16 2017-06-09 海泰纺织（苏州）有限公司 一种端巯基有机含磷‑氮‑硫酯化物及其制备方法和由其制得的阻燃聚酯纤维poy丝
CN106800574A (zh) * 2017-01-16 2017-06-06 海泰纺织（苏州）有限公司 一种端羧基有机含磷‑氮‑硫酯化物及其制备方法和由其制得的阻燃涤纶织物
CN106866740B (zh) * 2017-01-16 2019-01-15 东华大学 一种酯化物及其制备方法
CN106866734B (zh) * 2017-01-16 2019-06-11 东华大学 一种端基为酸性基团的有机含磷-氮酯化物及其制备方法
CN106831552B (zh) * 2017-01-16 2019-08-16 东华大学 一种端基为巯基的有机含氮-硫酯化物及其制备方法
CN106866517B (zh) * 2017-01-16 2019-09-17 东华大学 一种端基为羧酸基的有机含氮-硫酯化物及其制备方法
CN106866516B (zh) * 2017-01-16 2019-09-17 东华大学 一种端基为羧酸基的有机含氮酯化物及其制备方法
DE102018222396A1 (de) 2018-12-20 2020-06-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Phosphorhaltige Polyacrylamide und deren Verwendung als Flammschutzmittel
WO2021254993A1 (fr) 2020-06-17 2021-12-23 Renolit Se Acrylate résistant à la flamme

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