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WO2019048308A1 - Compositions de polyamide ignifuges ayant une résistance à la déformation à chaud élevée et leur utilisation - Google Patents

Compositions de polyamide ignifuges ayant une résistance à la déformation à chaud élevée et leur utilisation Download PDF

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Publication number
WO2019048308A1
WO2019048308A1 PCT/EP2018/073228 EP2018073228W WO2019048308A1 WO 2019048308 A1 WO2019048308 A1 WO 2019048308A1 EP 2018073228 W EP2018073228 W EP 2018073228W WO 2019048308 A1 WO2019048308 A1 WO 2019048308A1
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Prior art keywords
component
flame
polyamide compositions
compositions according
proportion
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Ceased
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PCT/EP2018/073228
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German (de)
English (en)
Inventor
Harald Bauer
Sebastian HÖROLD
Martin Sicken
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Avient Switzerland GmbH
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Clariant Plastics and Coatings Ltd
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Priority to EP18762269.1A priority Critical patent/EP3679092A1/fr
Publication of WO2019048308A1 publication Critical patent/WO2019048308A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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 present invention relates to flame-retardant polyamide compositions and moldings produced therefrom, which are characterized by a very good flame retardancy, a high heat resistance and very good electrical properties.
  • Flammable plastics generally have to be equipped with flame retardants in order to achieve the high flame retardance requirements demanded by plastics processors and in part by the legislation. Preference - also for ecological reasons - are non-halogenated
  • phosphinates the salts of phosphinic acids (phosphinates) have proven to be particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A).
  • dialkylphosphinates containing a small amount of selected telomers are suitable as flame retardants for polymers, the polymer only undergoing very little degradation upon incorporation of the flame retardant into the polymer matrix.
  • Flame retardants must often be added in high doses to ensure sufficient flame retardancy of the plastic according to international standards sure. Due to their chemical reactivity, which is required for the flame retardancy at high temperatures, can
  • Flame retardants especially at higher dosages, affect the processing stability of plastics. It can lead to increased polymer degradation, crosslinking reactions, outgassing or discoloration.
  • X-ray reflections of high-temperature modifications of aluminum salts of phosphinic acids are known from WO 98/03515 A1. These phosphinic acid salts are produced at high temperature.
  • polyamide compositions based on phosphinate-containing flame retardant systems which have all the aforementioned properties simultaneously and in particular good electrical properties (GWFI, CTI), excellent heat resistance (HDT-A) and a high
  • the invention therefore flame retardant
  • component A Fillers and / or reinforcing materials, preferably glass fibers, as component B,
  • Phosphinic acid salt of the formula (I) as component C Phosphinic acid salt of the formula (I) as component C.
  • Ri and R2 are ethyl
  • M is Al, Fe, TiOp or Zn
  • n 2 to 3, preferably 2 or 3
  • R 3 is ethyl
  • Met is Al, Fe, TiOq or Zn
  • n 2 to 3, preferably 2 or 3
  • the powder X-ray diffraction pattern of the compositions contains the following reflexes:
  • the X-ray spectra are taken with an X-ray powder diffractometer
  • the sample is irradiated with Cu-K-alpha radiation and the step time is 1 second.
  • Preferred novel polyamide compositions are those whose X-ray powder diffractogram contains the following reflections: in the angular range 2 ⁇ of 9.099 ° to 9.442 °, of 18.619 ° to 18.984 ° and of 26.268 ° to 26.679 °.
  • the proportion of component A is usually 25 to 95 wt .-%, preferably 25 to 75 wt .-%. In the polyamide composition according to the invention, the proportion of
  • Component B usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.
  • the proportion of component C is usually 1 to 35 wt .-%, preferably 5 to 20 wt .-%.
  • the proportion of component D is usually 0.01 to 3 wt .-%, preferably 0.05 to
  • the proportion of component E is usually 0.001 to 1 wt .-%, preferably 0.01 to
  • the percentages for the proportions of components A to E are based on the total amount of the polyamide composition.
  • the proportion of component A is from 25 to 75% by weight
  • the proportion of component B is from 20 to 40% by weight
  • Preferred salts of component C are those in which M m + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • Preferably used salts of component D are zinc, iron or
  • Preferably used salts of component E are those in which Met n + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • the above-described flame retardant polyamide compositions contain inorganic phosphonate as further component F. The use of the inventively used as component F.
  • the inorganic phosphonate (component F) preferably corresponds to the general formulas (IV) or (V)
  • the inorganic phosphonate (component F) is preferably aluminum phosphite [Al (H2PO3) 3], secondary aluminum phosphite [Al2 (HPO3) 3], basic aluminum phosphite [Al (OH) (H2PO3) 2 * 2aq],
  • the inorganic phosphonate (component F) is preferably also aluminum phosphites of the formulas (VI), (VII) and / or (VIII)
  • Aluminum phosphite tetrahydrate [Al 2 (HPO 3) 3 * 4aq] to give aluminum phosphonate, Al 7 (HPO 3 ) 9 (OH) 6 (1,6-hexanediamine) i, 5 * 12H 2 O, by ⁇ 2 ( ⁇ 3 ) 3 * ⁇ 2 ⁇ 3 * ⁇ 2 ⁇ with x 2,27 - 1 and / or AUHePieOis.
  • Preferred inorganic phosphonates are water-insoluble or sparingly soluble salts.
  • Particularly preferred inorganic phosphonates are aluminum, calcium and zinc salts.
  • component F is a
  • Reaction product of phosphorous acid and an aluminum compound Reaction product of phosphorous acid and an aluminum compound.
  • Particularly preferred components F are aluminum phosphites with the
  • the preparation of the preferably used aluminum phosphites is carried out by reacting an aluminum source with a phosphorus source and optionally a template in a solvent at 20-200 ° C for a period of up to 4 days.
  • the aluminum source and the phosphorus source are mixed for 1 to 4 hours, heated under hydrothermal conditions or at reflux, filtered off, washed and z. B. at 1 10 ° C dried.
  • Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
  • Preferred sources of phosphorus are phosphorous acid, (acidic)
  • Preferred Alkaliphosphite are disodium phosphite, dinat umphosphithydrat, trisodium phosphite, Kaliumhydrogenphosphit Preferred Dinatriumphosphithydrat is Brüggolen ® H10 Fa. Brüggemann.
  • Preferred templates are 1, 6-hexanediamine, guanidine carbonate or ammonia.
  • Preferred alkaline earth metal phosphite is calcium phosphite.
  • the preferred ratio of aluminum to phosphorus to solvent is 1: 1: 3.7 to 1: 2.2: 100 mol.
  • the ratio of aluminum to template is 1: 0 to 1: 17 mol.
  • the preferred pH of the reaction solution is 3 to 9.
  • Preferred solvent is water.
  • the same salt of phosphinic acid as the phosphorous acid is used in the application, so z.
  • phosphinic acid aluminum diethylphosphinate together with aluminum phosphite or Zinkdiethylphosphinat together with zinc phosphite.
  • the above-described flame retardant polyamide compositions contain a component F
  • Me is Fe, TiOr, Zn or in particular Al,
  • o is 2 to 3, preferably 2 or 3
  • Preferred compounds of the formula III are those in which Me is O + Zn 2+ , Fe 3+ or in particular Al 3+ .
  • Component F is preferably in an amount of 0.005 to 10 wt .-%, in particular in an amount of 0.02 to 5 wt .-%, based on the
  • the flame-retardant polyamide compositions according to the invention have a high heat distortion temperature (HDT-A) according to DIN EN ISO 75-3 of at least 280 ° C., preferably of at least 290 ° C. and more preferably of at least 300 ° C.
  • HDT-A high heat distortion temperature
  • Polyamide compositions having a Comparative Tracking Index measured according to the International Electrotechnical Commission Standard IEC-601 12/3, of greater than or equal to 500 volts.
  • Polyamide compositions achieve a rating of V0 according to UL-94, in particular measured on moldings of 3.2 mm to 0.4 mm thickness.
  • Polyamide compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 of at least 960 ° C, in particular measured
  • the polyamide compositions according to the invention contain as component A one or more thermoplastic polyamides having a melting point of greater than or equal to 290 ° C.
  • the melting point is determined by means of differential scanning calorimetry (DSC) at a heating rate of 10 K / second.
  • thermoplastic polyamides are based on Hans
  • inventively preferred polyamides can according to various aspects
  • Processes are prepared and synthesized from very different building blocks and in a particular application alone or in combination with
  • Processing aids, stabilizers or polymeric alloying partners, preferably elastomers, to materials with specially set property combinations are equipped. Also suitable are blends with proportions of other polymers, preferably of polyethylene, polypropylene, ABS, it being possible where appropriate to use one or more compatibilizers.
  • Properties of the polyamides can be improved by adding elastomers, for. In terms of impact strength, especially if they are reinforced polyamides. The multitude of possible combinations enables a very large number of products with different properties.
  • Monomerbausteine various chain regulators for setting a desired molecular weight or monomers with reactive groups for later intended post-treatments can be used.
  • polyamides to be used as component A are partially crystalline and aromatic or partially aromatic polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
  • educts are mainly aromatic dicarboxylic acids, preferably isophthalic acid and / or terephthalic acid or their polyamide-forming derivatives, such as salts, into consideration, alone or in combination with aliphatic
  • Dicarboxylic acids or their polyamide-forming derivatives preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, together with aliphatic and / or aromatic diamines, are preferred
  • Tetramethylenediamine Tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and
  • Copolyamides of several of the monomers mentioned are
  • aromatic and partially aromatic polyamides ie compounds in which at least some of the repeat units are composed of aromatic structural units.
  • obtained molded body reached at least 290 ° C.
  • aromatic polyamides starting from xylylenediamine and adipic acid; or polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as modifier, e.g. As poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide, block copolymers of the aforementioned polyamides with Polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
  • component A is an aromatic or partially aromatic polyamide or a mixture of a plurality of aromatic or partially aromatic polyamides or a mixture of polyamide 6.6 and one or more aromatic or partially aromatic polyamides.
  • thermoplastic polyamide in addition to the thermoplastic polyamide in a preferred embodiment
  • Embodiment additionally to be used polymers conventional additives, in particular mold release agents, stabilizers and / or flow aids can be added in the melt or applied to the surface.
  • thermoplastic polyamides of component A may be synthetically z. B. from petrochemical raw materials and / or chemical or biochemical processes resulting from renewable raw materials
  • component B fillers and / or preferably reinforcing materials are used, preferably glass fibers. It is also possible to use mixtures of two or more different fillers and / or reinforcing materials.
  • Preferred fillers are mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas, nanoscale minerals, particularly preferably montmorillonites or nano-boehmites, magnesium carbonate, chalk, feldspar, glass beads and / or barium sulfate. Particular preference is given to mineral particulate fillers based on talc, wollastonite and / or kaolin.
  • needle-shaped mineral fillers are also particularly preferably used. Under needle-shaped mineral fillers according to the invention a mineral filler with pronounced needle-like character understood. Preferred are needle-shaped wollastonites.
  • the mineral has a length to diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1.
  • the average particle size of the acicular mineral fillers used according to the invention as component B is preferably less than 20 ⁇ m, more preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m, determined using a CILAS granulometer.
  • the components B preferably used according to the invention are reinforcing materials. This may, for example, to
  • Reinforcement based on carbon fibers and / or glass fibers act.
  • the filler and / or reinforcing material may in a preferred
  • Be surface-modified embodiment preferably with a
  • Adhesive or a primer system particularly preferably on
  • Silane In particular when glass fibers are used, in addition to silanes, polymer dispersions, film formers, branching agents and / or
  • Fiber processing aids are used.
  • the glass fibers preferably used according to the invention as component B may be short glass fibers and / or long glass fibers. As short or long glass fibers, cut fibers can be used. Short glass fibers can also be used in the form of ground glass fibers.
  • glass fibers can also be used in the form of continuous fibers, for example in the form of rovings, monofilaments,
  • Filament yarns or twines or glass fibers can be used in the form of textile fabrics, for example as glass fabrics, as
  • Glass braid or as a glass mat Glass braid or as a glass mat.
  • Polyamide matrix range from 0.05 to 10 mm, preferably from 0.1 to 5 mm. After incorporation into the polyamide matrix, the length of the glass fibers has decreased. Typical fiber lengths for short glass fibers after the
  • Incorporation into the polyamide matrix ranges from 0.01 to 2 mm, preferably from 0.02 to 1 mm.
  • the diameters of the individual fibers can vary within wide ranges. Typical diameters of the individual fibers range from 5 to 20 ⁇ m.
  • the glass fibers can have any cross-sectional shapes, for example round, elliptical, n-cornered or irregular cross-sections. Glass fibers with mono- or multilobal cross-sections can be used.
  • Glass fibers can be used as continuous fibers or as cut or ground glass fibers.
  • the glass fibers themselves can be selected, for example, from the group of E-glass fibers, A-glass fibers, C-glass fibers, D-glass fibers, M-glass fibers, S-glass fibers,
  • the glass fibers are preferably provided with a size which preferably contains polyurethane as film former and aminosilane as adhesion promoter.
  • Particularly preferably used E glass fibers have the following chemical
  • R glass fibers have the following chemical composition: S1O2 50-65%; AI2O3 20-30%; CaO 6-16%; MgO 5-20%; Na 2 O 0.3-0.5%; K2O 0.05-0.2%; Fe 2 Os 0.2-0.4%, T1O2 0.1-0.3%.
  • Particularly preferably used ECR glass fibers have the following chemical composition: S1O2 57.5-58.5%; AI2O3 17.5-19.0%; CaO 11, 5-13.0%; MgO 9.5-1 1, 5.
  • Salts of diethylphosphinic acid with fractions of the phosphinic and phosphonic acid salts used according to the invention as components D and E are known flame retardants.
  • the preparation of this combination of substances is z. B. in US 7,420,007 B2 described.
  • Component C may contain small amounts of salts of component D and salts of component E, for example up to 10 wt .-% of
  • Component D preferably 0.01 to 6 wt .-%, and in particular 0.2 to 2.5 wt .-% thereof, and up to 10 wt .-% of component E, preferably 0.01 to 6 wt .-% , And in particular 0.2 to 2.5 wt .-% thereof based on the amount of components C, D and E.
  • Ethylphosphonic acid are as additives to diethylphosphinates in
  • Flame retardants for polymeric molding compositions also known, for example from WO 2016/065971 A1.
  • components C, D and E are in particulate form, the average particle size (dso) being 1 to 100 ⁇ m.
  • the salts of diethylphosphinic acid used according to the invention as component C are preferably prepared according to the method described in DE 103 59 815 A1
  • the polyamide compositions according to the invention may contain as component G further additives.
  • Preferred components G for the purposes of the present invention are antioxidants, UV stabilizers,
  • Gamma ray stabilizers Gamma ray stabilizers, hydrolysis stabilizers, co-stabilizers for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers,
  • the further additives are known per se as additives to polyamide compositions and can be used alone or mixed or in the form of masterbatches.
  • flame retarded polyamide composition are processed. It is thus possible to mix the components into the polyamide melt at the beginning or at the end of the polycondensation or in a subsequent compounding process. Furthermore, there are processing processes in which individual components are added later. This is especially practiced when using pigment or additive masterbatches. In addition, there is the possibility, in particular powdered components on by the
  • two or more of the components of the polyamide compositions of the present invention may be combined by mixing prior to incorporation into the polyamide matrix.
  • conventional mixing units can be used, in which the components in a suitable mixer, for. B. 0.01 to 10 hours at 0 to 300 ° C mixed.
  • Polyamide compositions can also be prepared granules, which can then be introduced into the polyamide matrix.
  • two or more components of the invention are also be prepared granules, which can then be introduced into the polyamide matrix.
  • Polyamide composition with granulation and / or binder in a suitable mixer or a granulating are processed into granules.
  • the initially formed crude product can be dried in a suitable dryer or tempered for further grain buildup.
  • the polyamide composition of the present invention or two or more components thereof may be prepared by roll compaction in one embodiment.
  • the polyamide composition according to the invention or two or more components thereof may in one embodiment be prepared by mixing, extruding, chopping (or breaking) the ingredients.
  • the polyamide composition of the present invention or two or more components thereof may be prepared by spray granulation in one embodiment.
  • the flame-retardant polymer molding composition according to the invention is preferably in granular form, for. B. as an extrudate or as a compound before.
  • the granules preferably have a cylindrical shape with a circular, elliptical or irregular base, spherical shape, pillow shape, cube shape, cuboid shape, prism shape.
  • Typical length to diameter ratio of the granules are 1 to 50 to 50 to 1, preferably 1 to 5 to 5 to 1.
  • the granules preferably have a diameter of 0.5 to 15 mm, more preferably of 2 to 3 mm and preferably a length of 0.5 to 15 mm, particularly preferably 2 to 5 mm.
  • the invention also relates to molded parts produced from the above-described flame-retardant polyamide composition comprising the components A, B, C, D and E and optionally components F and / or G.
  • the molded parts according to the invention may be any desired formations. Examples thereof are fibers, films or moldings obtainable from the flame-retardant polyamide molding compositions according to the invention by any desired molding processes, in particular by injection molding or extrusion.
  • the preparation of the flame-retardant polyamide molded body according to the invention can be carried out by any desired molding process. Examples include injection molding, pressing, foam injection, gas injection molding, blow molding,
  • the molded parts are preferably injection-molded parts or extruded parts.
  • the flame-retardant polyamide compositions according to the invention are suitable for the production of fibers, films and moldings, in particular for applications in the electrical and electronics sector.
  • the invention preferably relates to the use of the flame-retardant polyamide compositions according to the invention in or for connectors, current-carrying parts in power distributors (Fl protection), circuit boards, potting compounds, power connectors, circuit breakers, lamp housings, LED housings,
  • Capacitor housings bobbins and fans, protective contacts, plugs, in / on boards, housings for plugs, cables, flexible printed circuit boards, charging cables for mobile phones, engine covers or textile coatings.
  • the invention likewise preferably relates to the use of the flame-retardant polyamide compositions according to the invention for the production of Moldings in the form of components for the electrical / electronics sector,
  • the wall thickness of the shaped bodies according to the invention can typically be up to 10 mm. Particularly suitable are moldings with less than 1.5 mm wall thickness, more preferably less than 1 mm wall thickness and particularly preferably less than 0.5 mm wall thickness.
  • Polyamide 6T / 6.6 (melting range 310-320 ° C): Vestamid ® HT plus 1000 (Evonik)
  • Polyamide 6T / 6I (amorphous): Grivory ® G21, (EMS)
  • Twin-screw extruder (type Leistritz ZSE 27 / 44D) incorporated at temperatures of 310 to 330 ° C.
  • the glass fibers were over a second Side feeder added.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
  • Injection molding machine type Arburg 320 C Allrounder
  • mass temperatures 300 to 320 ° C to test specimens processed and based on the UL 94 test
  • the Glow Wire Flammability Index (GWIT Index) was standardized
  • the heat deflection temperature (HDT) was determined according to DIN EN ISO 75-3.
  • Test specimen height is thereby applied to obtain a so-called edge fiber tension ⁇ of 1, 80 (Method A), 0.45 (Method B) or 8.00 N / mm 2 (Method C) by weights and / or springs of a force. Subsequently, the loaded samples are subjected to heating at a constant heating rate of 120 K / h (or 50 K / h). Achieves the deflection of the sample one
  • Polyamide compositions are measured using an X-ray powder diffractometer (XTert-MPD, Phillips). The sample was irradiated with Cu-K-alpha radiation and the step time was 1 second. All tests of the respective series were carried out under similar conditions (such as temperature programs, screw geometries and injection molding parameters), unless otherwise stated.
  • XTert-MPD X-ray powder diffractometer
  • Example 5 The Polyannidzusannnneneren of Examples 1 to 5 according to the invention are molding compositions which reach the fire class UL 94 V-0 at 0.4 mm, while having CTI 600 volts, GWFI 960 ° C and HDT-A 290 ° C.
  • component F in Example 5 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.
  • PA 6T / 6I 58 58 58 58 58 58 55 58 B glass fibers 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 30 HP3610
  • the Polyannidzusannnneneren of Examples 6 to 10 according to the invention are molding compositions which reach the fire class UL 94 V-0 at 0.4 mm, while having CTI 600 volts, GWFI 960 ° C and HDT-A 300 ° C.
  • the addition of component F in Example 10 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des compositions de polyamide ignifuges contenant du polyamide ayant un point de fusion supérieur ou égal à 290 °C en tant que constituant A, des substances de charge et/ou des substances de renfort en tant que constituant B, un sel d'acide phosphinique de formule (I) en tant que constituant C, où R1 et R2 sont éthyle, M est Al, Fe, TiOp ou Zn, m vaut de 2 à 3 et p = (4 - m) / 2, un composé choisi dans le groupe des sels d'Al, de Fe, de TiOp ou de Zn de l'acide éthylbutylphosphinique, de l'acide dibutylphosphinique, de l'acide éthylhexylphosphinique, de l'acide butylhexylphosphinique et/ou de l'acide dihexylphosphinique en tant que constituant D et un sel d'acide phosphonique de formule (II) en tant que constituant E, où R3 est éthyle, Met est Al, Fe, TiOq ou Zn, n vaut de 2 à 3 et q = (4 - n) / 2, le diagramme de diffraction X sur poudre des compositions présentant les réflexions suivantes : dans le domaine angulaire 2θ de 9,099° à 9,442°, de 18,619° à 18,984° et de 26,268° à 26,679° et/ou dans le domaine angulaire 2θ de 5,112° à 5,312°, de 6,097° à 6,297°, de 10,082° à 10,282°, de 10,350° à 10,550° et de 12,308° et 12,508° et/ou dans le domaine angulaire 2θ de 8,300° à 8,500° et de 14,765° à 15,076°. Ces compositions de polyamide peuvent être employées pour la production de fibres, de films et de corps moulés, notamment pour des applications dans les domaines électrique et électronique.
PCT/EP2018/073228 2017-09-07 2018-08-29 Compositions de polyamide ignifuges ayant une résistance à la déformation à chaud élevée et leur utilisation Ceased WO2019048308A1 (fr)

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DE102018220696A1 (de) 2018-11-30 2020-06-04 Clariant Plastics & Coatings Ltd Flammschutzmittelmischungen, flammhemmende Polymerzusammensetzungen, damit ausgerüstete Kabel und deren Verwendung
CN111100449A (zh) * 2019-12-03 2020-05-05 天津金发新材料有限公司 一种聚酰胺组合物及其制备方法
CN116284118A (zh) * 2022-09-30 2023-06-23 金发科技股份有限公司 一种球状膦酸盐阻燃剂及其制备方法和应用

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