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WO1998036022A1 - Matieres de moulage thermoplastiques ignifugees - Google Patents

Matieres de moulage thermoplastiques ignifugees Download PDF

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Publication number
WO1998036022A1
WO1998036022A1 PCT/EP1998/000595 EP9800595W WO9836022A1 WO 1998036022 A1 WO1998036022 A1 WO 1998036022A1 EP 9800595 W EP9800595 W EP 9800595W WO 9836022 A1 WO9836022 A1 WO 9836022A1
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Prior art keywords
polyamide
weight
molding compositions
thermoplastic molding
compositions according
Prior art date
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PCT/EP1998/000595
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German (de)
English (en)
Inventor
Martin Klatt
Stefan Grutke
Thomas Heitz
Volker Rauschenberger
Thomas Plesnivy
Peter Wolf
Josef WÜNSCH
Michael Fischer
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BASF SE
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BASF SE
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Priority claimed from DE1997105998 external-priority patent/DE19705998A1/de
Priority claimed from DE1997114900 external-priority patent/DE19714900A1/de
Application filed by BASF SE filed Critical BASF SE
Publication of WO1998036022A1 publication Critical patent/WO1998036022A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • the invention relates to the use of the thermoplastic molding compositions according to the invention for the production of fibers, films and moldings of any kind, and to the moldings obtainable here.
  • delaminated layered silicates in polyamides is e.g. from E.P. Giannelis, Adv. Mater. 8, 29-35, 1996.
  • caprolactam or caprolactam dimer is formed (by partial cleavage of the polyamide), whereby a coating is formed in the mold and the mechanical and Flame retardant properties deteriorate due to, among other things, molecular weight reduction.
  • this coating formation leads, for example, to incorrect formwork only for polyamides made from caprolactam, but generally for polyamides made from actam monomers.
  • a reduction in the oligomer or monomer content is achieved by this procedure, but the oligomers which are partially embedded in the minerals or adsorbed on the surface are only bound physically (not chemically); i.e. the oligomers remain extractable.
  • the mechanical properties such as elongation at break and impact strength are unsatisfactory, as is heat resistance (HDT).
  • reinforced flame-retardant polyamides are required for many applications, the addition results e.g. of glass fibers in poor fire behavior.
  • the cause lies in a so-called wick effect of the glass fibers, whereby the test specimen continues to burn even after the pilot flame has been removed.
  • the present invention was therefore based on the object of providing flame-retardant polyamide molding compositions, in particular those composed of lactam monomers, which exhibit less blooming during processing and permit a higher continuous service temperature with acceptable mechanical and flame-retardant properties.
  • Another object of the present invention was to provide flame-retardant polyamides which are comparable in mechanical properties to fiber-reinforced and flame-retardant polyamide molding compositions (in particular in terms of rigidity and tear resistance), but better phosphorus stability and fire behavior, in particular for have very thin-walled moldings.
  • the combination of red phosphorus with delaminated phyllosilicates leads to better phosphorus stability, so that moldings can be used in environments with high atmospheric humidity even at elevated temperatures.
  • the flame retardant properties are significantly improved in the case of very thin-walled molded parts, the mechanical properties being comparable to fiber-reinforced polyamide molding compounds.
  • the molding compositions according to the invention contain 10 to 98, preferably 20 to 97 and in particular 30 to 95% by weight of a polyamide.
  • the polyamides of the molding compositions according to the invention generally have a viscosity number of 90 to 350, preferably 110 to 240 ml / g, determined in a 0.5 wt. -% solution in 96% by weight sulfuric acid at 25 ° C according to ISO 307.
  • Semi-crystalline or amorphous resins with a molecular weight (weight average) 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 which are derived from lactams with 7 to 13 ring members, such as polycaprolactam, polycapryllactam and polylaurinlactam, and polyamides which are obtained by reacting dicarboxylic acids with diamines.
  • Alkane dicarboxylic acids with 4 to 14, in particular 6 to 10 carbon atoms and aromatic dicarboxylic acids can be used as dicarboxylic acids. Only adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, naphthalenedicarboxylic acid and terephthalic and / or isophthalic acid may be mentioned here as acids.
  • Particularly suitable diamines are alkane diamines with 4 to 14, in particular 6 to 8, carbon atoms and m-xylylenediamine, di- (4-aminophenyl) methane, di- (4-aminocyclohexyl) methane, 2,2-di- (4-aminophenyl) ) propane or 2,2-di- (4-aminocyclohexyl) propane.
  • Preferred polyamides are polyhexamethylene adipic acid amide, polyhexamethylene sebacic acid amide and polycaprolactam as well as copolyamides 6/66, in particular with a proportion of 5 to 95% by weight of caprolactam units.
  • Polyamides may also be mentioned, e.g. can be obtained by condensing 1,4-diaminobutane with adipic acid at elevated temperature (polyamide-4, 6). Manufacturing processes for polyamides of this structure are e.g. 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 aforementioned monomers, or mixtures of two or more polyamides, the mixing ratio being arbitrary.
  • those partially aromatic copolyamides such as PA 6 / 6T and PA 66 / 6T have proven particularly advantageous, the triamine content of which is less than 0.5, preferably less than 0.3% by weight (see EP-A 299 444).
  • the preferred partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196.
  • mixtures (blends) of such polymers can also be used.
  • polyamides which contain at least 5, preferably 10% by weight, based on 100% by weight of A), of units which are derived from Lac am monomers.
  • Suitable lactam monomers have 7 to 13 ring members.
  • Preferred polyamides contain units which are preferably derived from laurolactam, acryllactam, ⁇ -caprolactam and butyrolactam, polyamide 6 and polyamide 12 and copolyamides 6/66 and copolyamides from caprolactam and terephthalic acid / isophthalic acid (for example PA 6 / 6T, PA 6 / 61) are preferred.
  • Copolyamides 6/66 are particularly preferred, the proportion of caprolactam units preferably being 5 to 95% by weight, in particular 10 to 90% by weight, based on the copolyamide. Mixtures of such polyamides can of course also be used. Also preferred are polamides A, which consist of a mixture (so-called blends, based on 100% by weight A)
  • AI 5 to 95% by weight, preferably 10 to 90% by weight, of a polyamide obtainable from lactam monomers, preferably polyamide 6, with
  • A2) 5 to 95% by weight, preferably 10 to 90% by weight, of a polyamide different from AI)
  • Suitable as component A2) are semicrystalline or amorphous resins, as already stated above, which do not contain any units which are derived from lactam monomers.
  • the molding compositions according to the invention contain 1 to 20, preferably 2 to 15 and in particular 3 to 10% by weight of red phosphorus as component B).
  • the average particle size (dso) of the phosphor articles distributed in the molding compositions is usually in the range up to 2 mm, preferably 0.0001 to 0.5 mm.
  • the phosphorus in powder form can easily be incorporated into the molding compositions according to the invention, the phosphorus usually being in the form of desensitized phosphorus (see EP-A 176 836, EP-A 384 232 and DE-A 19 648 503).
  • Concentrates of phlegmatized phosphorus are e.g. suitable in a polyamide or an elastomer, which can have phosphorus contents of up to 60% by weight.
  • the molding compositions according to the invention contain 0.1 to 15, preferably 1 to 10 and in particular 2 to 9% by weight of a delaminated layered silicate (phyllosilicate).
  • Layered silicate is generally understood to be silicates in which the SiO 4 tetrahedra are connected in two-dimensional infinite networks. (The empirical formula for the anion is (Si 2 0s 2 ") n ) • The individual layers are connected to each other by the cations between them, whereby mostly Na, K, Mg, Al or / and Ca in the naturally occurring cations Layered silicates are available.
  • Examples of synthetic and natural layered silicates are montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allevardite, amesite, hectorite, fluorohectorite, saponite, beidellite, talc, nontronite, stevensite, vermiculite, mica , Halloysite and fluorine-containing synthetic talc types.
  • a delaminated layered silicate in the sense of the invention is to be understood as meaning layered silicates in which the layer spacings are initially increased by reaction with so-called hydrophobizing agents and, if appropriate, subsequent addition of monomers (so-called swelling, for example with so-called AH salts).
  • the layer thicknesses of such silicates before delamination are usually from 5 to 100 ⁇ , preferably 5 to 50 ⁇ and in particular 8 to 20 ⁇ .
  • the layers are delaminated, which preferably result in a layer spacing of at least 40 ⁇ , preferably at least 50 ⁇ , in the molded article by making up the hydrophobicized and optionally swollen layered silicate with polyamides.
  • hydrophobizing agents which are often also referred to as onium ions or onium salts.
  • the cations of the layered silicates are replaced by organic hydrophobicizing agents, the type of organic residue making it possible to set the desired layer spacings, which depend on the type of the particular monomer or polymer into which the layered silicate is to be incorporated.
  • the metal ions can be exchanged completely or partially. A complete exchange of the metal ions is preferred.
  • the amount of exchangeable metal ions is usually given in milliequivalents (meq) per 100 g of layered silicate and referred to as the ion exchange capacity.
  • Layered silicates with a cation exchange capacity of at least 50, preferably 80 to 130 meq / 100 g are preferred.
  • Suitable organic water repellents are derived from oxonium, ammonium, phosphonium and sulfonium ions, which can carry one or more organic radicals.
  • Suitable hydrophobicizing agents are those of the general formula I and / or II:
  • R 1 , R 2 , R 3 , R 4 independently of one another are hydrogen, a straight-chain branched, saturated or unsaturated hydrocarbon radical having 1 to 40, preferably 1 to 20, carbon atoms, which can optionally carry at least one functional group or 2 of the radicals are linked to one another, in particular to form a heterocyclic radical having 5 to 10 carbon atoms,
  • n for an integer from 1 to 5, preferably 1 to 3 and
  • Suitable functional groups are hydroxyl, nitro or sulfo groups, carboxyl groups being particularly preferred, since such functional groups result in improved binding to the end groups of the polyamide.
  • Suitable anions Z are derived from proton-providing acids, in particular mineral acids, with halogens such as chlorine, bromine, fluorine, iodine, sulfate, sulfonate, phosphate, phosphonate, phosphite and carboxylate, in particular acetate, being preferred.
  • the layered silicates used as starting materials are generally implemented in the form of a suspension.
  • the preferred suspending agent is water, optionally in a mixture with alcohols, especially lower alcohols with 1 to 3 carbon atoms. It may be advantageous to use a hydrocarbon, for example heptane, together with the aqueous medium, since the hydrophobicized layered silicates are usually more compatible with hydrocarbons than with water.
  • suspending agents are ketones and hydrocarbons.
  • a water-miscible solvent is usually preferred.
  • the hydrophobicizing agent is added to the layered silicate, an ion exchange occurs, as a result of which the layered silicate usually precipitates out of the solution.
  • the metal salt formed as a by-product of the ion exchange is preferably water-soluble, so that the hydrophobicized layered silicate as a crystalline solid by e.g. Filtering can be separated.
  • the ion exchange is largely independent of the reaction temperature.
  • the temperature is preferably above the crystallization point of the medium and below its boiling point. In aqueous systems, the temperature is between 0 and 100 ° C, preferably between 40 and 80 ° C.
  • Alkylammonium ions are preferred for polyamides, which in particular by reacting suitable ⁇ -aminocarboxylic acids such as ⁇ -aminododecanoic acid, ⁇ -aminoundecanoic acid, ⁇ -aminobutyric acid, ⁇ -aminocaprylic acid or ⁇ -aminocaproic acid with customary mineral acids, for example hydrochloric acid, sulfuric acid or phosphoric acid or Methylating agents such as methyl iodide are available.
  • suitable ⁇ -aminocarboxylic acids such as ⁇ -aminododecanoic acid, ⁇ -aminoundecanoic acid, ⁇ -aminobutyric acid, ⁇ -aminocaprylic acid or ⁇ -aminocaproic acid
  • customary mineral acids for example hydrochloric acid, sulfuric acid or phosphoric acid or Methylating agents such as methyl iodide are available.
  • alkylammonium ions are laurylammonium, myristylammonium, palmitylammonium, stearylammonium, pyridinium, octadecylammonium, monomethyloctadecylammonium and dimethyloctadecylammonium ions.
  • the layered silicates After the hydrophobization, the layered silicates have a layer spacing of 10 to 50 ⁇ , preferably 13 to 40 ⁇ .
  • the layer spacing usually means the distance from the lower layer edge of the upper layer to the upper layer edge of the lower layer.
  • the layered silicate which has been rendered hydrophobic in the above manner can then be mixed in suspension or as a solid with the polyamide monomers or prepolymers and the polycondensation can be carried out in the customary manner.
  • the layer spacing is additionally increased by 10 to 150, preferably by 20 to 50 ⁇ .
  • the length of the leaf is usually up to 2000 ⁇ , preferably up to 1500 ⁇ .
  • the polycondensation is then carried out in the customary manner. The polycondensation is carried out particularly advantageously with simultaneous shear, preferably with shear stresses in accordance with DIN 11 443 of 10 to 10 5 Pa, in particular 10 2 to 10 4 Pa.
  • the additives D) can be added to the monomers or to the prepolymer melt (degassing extruder).
  • Another preferred preparation of the molding compositions according to the invention is the mixing of the individual components A) to D) by means of conventional devices such as, for example, Called extruders. After the extrusion, the extrudate is cooled and crushed.
  • the polyamide molding compounds can then be subjected to a further thermal treatment, i.e. subject to post-condensation in the solid phase.
  • a further thermal treatment i.e. subject to post-condensation in the solid phase.
  • tempering units such as Using a tumbler mixer or continuously and discontinuously operated tempering tubes, the molding compound in the respective processing form is tempered until the desired viscosity number VZ or relative
  • Viscosity ⁇ rel of the polyamide is reached.
  • the temperature range of the tempering depends on the melting point of the pure component A). Preferred temperature ranges are 5 to 50, preferably 20 to 30 ° C. below the respective melting point of the pure components A).
  • the process is preferably carried out in an inert gas atmosphere, nitrogen and superheated steam being preferred as inert gases.
  • the residence times are generally from 0.5 to 50, preferably from 4 to 20 hours. Then molded parts are produced from the molding compositions using conventional devices.
  • the molding compositions according to the invention may contain 0 to 70, in particular up to 50% by weight of further additives and processing aids as component D).
  • Additional additives are, for example, in amounts of up to 40, preferably up to 30,% by weight of rubber-elastic polymers (often also referred to as impact modifiers, elastomers or rubbers).
  • these are copolymers which are preferably composed of at least two of the following monomers: ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters with 1 to 18 C atoms in the alcohol component.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • EPM rubbers generally have practically no more double bonds, whereas EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • diene monomers for EPDM rubbers are conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms such as penta-1,4-diene, hexa-1,4-diene, hexa-1,5 -diene, 2, 5-dimethylhexa-l, 5-diene and octa-1, 4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cycloocta-dienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethyliden-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-decadiene or mixtures thereof.
  • conjugated dienes
  • Hexa-1,5-diene-5-ethylidene-norbornene and dicyclopentadiene are preferred.
  • the diene content of EPDM rubbers is preferred as 0.5 to 50, in particular 1 to 8 wt .-%, based on the total weight of the rubber.
  • EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as 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 can also contain dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids, e.g. Contain esters and anhydrides, and / or monomers containing epoxy groups.
  • dicarboxylic acid derivatives or monomers containing epoxy groups are preferably incorporated into the rubber by adding monomers of the general formulas I or II or III or IV containing dicarboxylic acid or epoxy groups to the monomer mixture:
  • R 1 to R 9 are hydrogen or alkyl groups with 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 are preferably 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 the 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 comes close to that of the free acids and is therefore referred to as 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 monomers containing acid anhydride groups and the remaining amount of (meth) acrylic acid esters.
  • Copolymers of are particularly preferred
  • n-butyl acrylate 1 to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • 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 processes known per se, preferably by static copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
  • Preferred elastomers are also emulsion polymers, the production of which e.g. Blackley in the monograph "Emulsion Polymerization" is described.
  • the emulsifiers and catalysts that can be used are known per se.
  • homogeneous elastomers or 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.
  • monomers for the production of the rubber part of the elastomers such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, Butadiene and isoprene and their mixtures called.
  • monomers for the production of the rubber part of the elastomers such as n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, Butadiene and isoprene and their mixtures called.
  • monomers can be copolymerized with further monomers such as, for example, styrene, acrylonitrile, vinyl ethers and further acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate.
  • the soft or rubber phase (with a glass transition temperature of below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two shells); in the case of multi-layer elastomers, several shells can also consist of a rubber phase.
  • one or more hard components are involved in the construction of the elastomer, these are generally made by polymerizing styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as main monomers. In addition, smaller proportions of further comonomers can also be used here.
  • emulsion polymers which have reactive groups on the surface.
  • groups are e.g. Epoxy, carboxyl, latent carboxyl, amino or amide groups as well as functional groups by the use of monomers of the general formula
  • R 10 is hydrogen or a C 1 -C 4 -alkyl group
  • R 11 is hydrogen, a C 1 -C 1 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a Cj . - to Cio-alkyl, a C_ to C ⁇ 2 aryl group or -OR 13
  • R 13 is a C 1 to C 6 alkyl or C 6 to C 1 aryl group, which may optionally be substituted by 0 or N-containing groups, a chemical bond, a Ci to Cio alkylene or C 6 -C 2 arylene group or
  • Z is a Ci to C ⁇ 0 alkylene or C 6 - to C ⁇ 2 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-diethyl) called amino) ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • Monomers acting as crosslinking agents are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
  • So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization.
  • Compounds are preferably used in which at least one reactive group polymerizes at approximately the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize).
  • the different rates of polymerization result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.
  • graft-crosslinking monomers examples include monomers containing allyl groups, 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 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.
  • graft crosslinking monomers for further details, reference is made here, for example, to US Pat. No. 4,148,846.
  • 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.
  • graft polymers with a core and at least one outer shell have the following structure:
  • graft polymers with a multi-layer structure instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of Bu-ta-1, 3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be prepared by using crosslinking monomers or monomers with 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,
  • the elastomers described can also be made 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 also preferred.
  • thermoplastic molding compositions according to the invention can contain stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation retarders and heat stabilizers are sterically hindered phenols, hydroquinones, copper compounds, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures 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.
  • Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants.
  • Sodium phenylphosphinate, PA22, aluminum oxide or silicon dioxide can be used as nucleating agents.
  • Lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (for example stearic acid or behenic acid), their salts (for example Ca or Zn stearate) and amide derivatives (for example ethylene-bis-stearylamide). or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) and low-molecular polyethylene or polypropylene waxes.
  • the molding compositions according to the invention can contain 0 to 50, preferably 5 to 40 and in particular 10 to 30% by weight of a fibrous or particulate filler.
  • Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.
  • the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.
  • Suitable silane compounds are those of the general formula III
  • ⁇ / 0 n an integer from 2 to 10, preferably 3 to 4 m an integer from 1 to 5, preferably 1 to 2 k 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 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on C) for surface coating.
  • Fibrous fillers with an average arithmetic fiber length of 150 to 300 ⁇ m, preferably 200 to 270 ⁇ m and in particular 220 to 250 ⁇ m are preferred.
  • the average diameter is generally from 3 to 30 ⁇ m, preferably from 8 to 20 ⁇ m and in particular from 10 to 14 ⁇ m.
  • the desired fiber length can e.g. can be adjusted by grinding in a ball mill, whereby a fiber length distribution arises.
  • the fiber content is usually determined after the polymer has been incinerated.
  • the ash residue is generally taken up in silicone oil and photographed at 10 20 ⁇ magnification of the microscope.
  • the length of at least 500 fibers can be measured on the images and the arithmetic mean (dso) can be calculated from them.
  • needle-shaped mineral fillers 15 which are mineral fillers with a pronounced needle-like character.
  • An example is needle-shaped wollastonite.
  • the mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
  • the mineral filler may optionally have been pretreated with the above-mentioned silane compounds; however, the pretreatment is not absolutely necessary.
  • Amorphous silica, magnesium carbonate (chalk), kaolin (in particular calcined kaolin), powdered quartz, mica, talc, feldspar and in particular calcium silicates such as wollastonite are suitable as particulate fillers.
  • the molding compositions according to the invention are notable for good phosphorus stability. Shaped bodies of the molding compositions according to the invention have a higher continuous use temperature in an environment with high atmospheric humidity and, at the same time, good mechanical properties.
  • the molding compositions according to the invention are furthermore notable for good processability (low mold coverage). Shaped bodies of the molding compositions according to the invention exhibit a higher continuous use temperature with reduced monomer formation and, at the same time, good mechanical and flame retardant properties. 0
  • the moldings have a 1 — E — 2-1— ⁇ 2 layer structure, 1 being the thermoplastic matrix and layer 2 being the delaminated layered silicate and n being an integer of at least 50, preferably at least 100. 5
  • the suspension was then filtered, the precipitate was cleaned with water and spray-dried.
  • Polyamide 66 with a viscosity number (VZ) of 152 ml / g (measured as a 0.5% by weight solution in 96% by weight H 2 S0 according to ISO 307).
  • Red phosphorus (containing 0.7% by weight of dioctyl phthalate as desensitizing agent) with an average particle size (dso) of 45 ⁇ m.
  • Components A / 1 to D) were made up on a twin-screw extruder (120 rpm, 30 kg / h) at 280 ° C., extruded and cooled and granulated in a water bath. The granules were dried at 80 ° C. in vacuo and processed to standard test specimens at 280 ° C. on an injection molding machine.
  • rods were hosed down and tested in accordance with UL 94 according to normal conditioning.
  • the extent of hydrolysis of the red phosphorus was determined by storage in water at 60 ° C for 100 days. For this purpose, standard small rods were injected, stored in water and then the content of soluble phosphorus compounds was determined quantitatively.
  • the modulus of elasticity was determined in accordance with ISO 527 and the tensile strength in accordance with ISO 527.
  • Component A / 3 contained 6.9% by weight of C, based on polyamide
  • the suspension was then filtered, the precipitate was cleaned with water and spray-dried.
  • VZ viscosity number
  • Polyamide 6 / 6T (30 units by weight, which are derived from ⁇ -caprolactam and 70% by weight, units which are derived from hexamethylene diamine and terephthalic acid) with a VZ of 150 ml / g according to ISO 307.
  • Red phosphorus (containing 0.7% by weight of dioctyl phthalate as
  • Desensitizing agent of average particle size (dso) of 45 microns.
  • D / 4 heat stabilizer based on copper Cu content: 0.76% by weight (Ultrabatch ® 61 from BASF AG).
  • Components A / 4 or A / 5 to D) were made up on a twin-screw extruder (200 rpm, 50 kg / h) at 280 ° C., extruded and cooled and pelletized in a water bath.
  • Granules were dried at 80 ° C in a vacuum and processed at 270 ° C on an injection molding machine.
  • a polyamide prepolymer with a VN of 80 ml / g was assembled with components B) to D) on a degassing extruder at 270 ° C., cooled and granulated.
  • the granules were discontinuously in a fixed annealing tube (double-walled, from the outside with oil to temperature heated glass tube of 120 mm inside diameter and 1000 mm length, which was flowed through with 120 1 / min superheated steam) to a VZ of 150 ml / g annealed (component A / 7).
  • the residence time was 12 hours.
  • Components A / 4 and A / 6 and the prepolymer of component A / 7 were extracted with water before they were mixed with components B) to D).
  • rods were hosed down and tested in accordance with UL 94 according to normal conditioning.
  • the residual extract (%) before the hot storage was determined by extraction of the granules (components A) to D)) with methanol (16 h). After the extraction, the methanol was separated off and the residual extract content (dimer, monomer and oligomer content) was determined gravimetrically.
  • granules were stored under nitrogen at 200 ° C. for 24 h and then extracted with methanol for 16 h. The methanol was then removed and the residual extract content was determined gravimetrically.
  • the E modulus was determined in accordance with ISO 527, and the tensile strength in accordance with ISO 527.

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

Abstract

L'invention concerne des matières de moulage thermoplastiques contenant: A) entre 10 et 98 % en poids d'un polyamide, B) entre 1 et 20 % en poids de phosphore rouge, C) entre 0,1 et 15 % en poids d'un silicate lamellaire délaminé (phyllosilicate), D) entre 0 et 70 % en poids d'autres additifs et auxiliaires de traitement, la somme des pour-cent en poids des constituants A) à D) s'élevant à 100 %.
PCT/EP1998/000595 1997-02-17 1998-02-04 Matieres de moulage thermoplastiques ignifugees Ceased WO1998036022A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE1997105998 DE19705998A1 (de) 1997-02-17 1997-02-17 Flammgeschützte thermoplastische Formmassen
DE19705998.8 1997-02-17
DE1997114900 DE19714900A1 (de) 1997-04-10 1997-04-10 Flammgeschützte thermoplastische Formmassen
DE19714900.6 1997-04-10

Publications (1)

Publication Number Publication Date
WO1998036022A1 true WO1998036022A1 (fr) 1998-08-20

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047662A1 (fr) * 1999-02-10 2000-08-17 Basf Aktiengesellschaft Nanocomposites thermoplastiques
WO2001090241A1 (fr) * 2000-05-19 2001-11-29 Bayer Aktiengesellschaft Compositions polymeres a resilience modifiee
FR2859814A1 (fr) * 2003-09-12 2005-03-18 Nexans Composition electriquement isolante et thermiquement resistante
CN100335551C (zh) * 2005-08-27 2007-09-05 西北师范大学 坡缕石乙烯－醋酸乙烯复合阻燃材料
CN100350015C (zh) * 2005-01-18 2007-11-21 西北师范大学 一种坡缕石复合阻燃剂
EP2305447A1 (fr) * 2009-10-05 2011-04-06 Basf Se Procédé de fabrication de composants à partir d'une masse de formage thermoplastique et composants constitué d'une masse de formage thermoplastique
EP2415827A1 (fr) * 2010-08-04 2012-02-08 Basf Se Polyamides ignifuges dotés de silicate en couche
US8772394B2 (en) 2005-01-17 2014-07-08 Dsm Ip Assets B.V. Heat stabilized moulding composition
US9745515B2 (en) 2002-10-31 2017-08-29 Commonwealth Scientific And Industrial Research Organisation Fire resistant material

Citations (2)

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Publication number Priority date Publication date Assignee Title
DE2551718A1 (de) * 1975-11-18 1977-06-02 Basf Ag Brandgeschuetzte polyamidformmassen
EP0312471A2 (fr) * 1987-10-12 1989-04-19 Rhone-Poulenc Chimie Compositions à base de polyamide ignifuge

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DE2551718A1 (de) * 1975-11-18 1977-06-02 Basf Ag Brandgeschuetzte polyamidformmassen
EP0312471A2 (fr) * 1987-10-12 1989-04-19 Rhone-Poulenc Chimie Compositions à base de polyamide ignifuge

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Title
GIANNELIS E P: "POLYMER LAYERED SILICATE NANOCOMPOSITES", ADVANCED MATERIALS, vol. 8, no. 1, 1 January 1996 (1996-01-01), pages 29 - 35, XP000551307 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000047662A1 (fr) * 1999-02-10 2000-08-17 Basf Aktiengesellschaft Nanocomposites thermoplastiques
US6673860B1 (en) 1999-02-10 2004-01-06 Basf Aktiengesellschaft Thermoplastic nanocomposites
WO2001090241A1 (fr) * 2000-05-19 2001-11-29 Bayer Aktiengesellschaft Compositions polymeres a resilience modifiee
US9745515B2 (en) 2002-10-31 2017-08-29 Commonwealth Scientific And Industrial Research Organisation Fire resistant material
FR2859814A1 (fr) * 2003-09-12 2005-03-18 Nexans Composition electriquement isolante et thermiquement resistante
WO2005027146A1 (fr) * 2003-09-12 2005-03-24 Nexans Composition electriquement isolante et thermiquement resistante
US8772394B2 (en) 2005-01-17 2014-07-08 Dsm Ip Assets B.V. Heat stabilized moulding composition
US8969460B2 (en) 2005-01-17 2015-03-03 Dsm Ip Assets B.V. Heat stabilized moulding composition
CN100350015C (zh) * 2005-01-18 2007-11-21 西北师范大学 一种坡缕石复合阻燃剂
CN100335551C (zh) * 2005-08-27 2007-09-05 西北师范大学 坡缕石乙烯－醋酸乙烯复合阻燃材料
EP2305447A1 (fr) * 2009-10-05 2011-04-06 Basf Se Procédé de fabrication de composants à partir d'une masse de formage thermoplastique et composants constitué d'une masse de formage thermoplastique
EP2415827A1 (fr) * 2010-08-04 2012-02-08 Basf Se Polyamides ignifuges dotés de silicate en couche

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