WO2003106547A2 - Compositions d'agents ignifugeants destinees a des demi-produits et des matieres a mouler polyolefiniques - Google Patents

Compositions d'agents ignifugeants destinees a des demi-produits et des matieres a mouler polyolefiniques Download PDF

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WO2003106547A2
WO2003106547A2 PCT/EP2003/006177 EP0306177W WO03106547A2 WO 2003106547 A2 WO2003106547 A2 WO 2003106547A2 EP 0306177 W EP0306177 W EP 0306177W WO 03106547 A2 WO03106547 A2 WO 03106547A2
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Prior art keywords
flame retardant
mass
melamine
retardant compositions
polyolefin
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PCT/EP2003/006177
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German (de)
English (en)
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WO2003106547A3 (fr
Inventor
Manfred Rätzsch
Markus Machherndl
Peter Breiteneder
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Agrolinz Melamin Gmbh
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Priority to AU2003242685A priority Critical patent/AU2003242685A1/en
Publication of WO2003106547A2 publication Critical patent/WO2003106547A2/fr
Publication of WO2003106547A3 publication Critical patent/WO2003106547A3/fr

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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
    • C08K3/38—Boron-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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34922—Melamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene

Definitions

  • the invention relates to flame retardant compositions for semi-finished polyolefin products and high-flame resistance molded materials with reduced corrosion during the melt processing of the polyolefin flame retardant mixtures.
  • Polyolefin compositions with halogen-containing flame retardants such as tris (tri-bromo neopentyl) phosphate (JP 11 255 970 A1), tetrabromobisphenol bis (2,3-dibromo propyl) ether (JP 11 255 969 A1) or hexabromocyclododecane (JP 2000 143 885 A1) have a high flame resistance, but the disadvantage is the interaction of small amounts of hydrogen bromide, which is formed at higher processing temperatures by partial decomposition of the flame retardants, with the HALS stabilizers used, which leads to a reduction in the UV stability of the products.
  • halogen-containing flame retardants such as tris (tri-bromo neopentyl) phosphate (JP 11 255 970 A1), tetrabromobisphenol bis (2,3-dibromo propyl) ether (JP 11 255 969 A1) or hexabro
  • flame retardant compositions for polyolefins the 42 mass% ammonium polyphosphate, 16 mass% polyamide 6 and 5 mass% melamine cyanurate (JP 2000 327 854) or 30 mass% ammonium polyphosphate, 3 mass% melamine cyanurate and 1 mass% zinc borate (JP 2000 160 031 A1), based in each case on the polyolefins used, in order to correspond to a classification V-0 in the UL 94 flame test.
  • the disadvantage is Corrosion effect of the flame retardant compositions during the melt processing of the polyofine flame retardant mixtures due to the high proportion of the mixtures in ammonium polyphosphate.
  • the aim of the invention is to provide flame retardant compositions for semi-finished polyolefin products and high-flame resistance molded materials with reduced corrosion during the melt processing of the polyolefin / flame retardant mixtures.
  • the object of the invention was modified by flame retardant compositions comprising a) 45 to 68% by mass of charring catalysts of the ammonium polyphosphate and / or zinc borate type, b) 15 to 30% by weight of blowing agent of the aminotriazine type, c) 15 to 30% by weight of crust former of the aminoplast type Aminoplasts and / or C -C 6 polyalcohols, and d) optionally 7 to 20% by mass of layered silicates, the blowing agents b) and / or the crust-forming agents c) being completely or partially intercalated in the intermediate layers of the layered silicates, and wherein the flame retardant compositions are present in proportions of 22 to 35% by mass in the polyolefin semi-finished products and moldings of high flame resistance.
  • Examples of semi-finished polyolefin products which can contain the flame retardant formulations according to the invention are foils, foam foils, plates, profiles, tubes, fibers, nonwovens, coatings and laminates.
  • polyolefin molding materials which can contain the flame retardant formulations according to the invention are products produced by injection molding, blow molding or by rotational molding.
  • the polyolefins containing flame retardant compositions in the semifinished polyolefin products or molded materials are preferably poly-C 2 -C 5 -olefins or copolymers of C 2 -C 5 - ⁇ -olefins and ⁇ -olefins having 2 to 18 C atoms of the type linear and / or branched polyethylene - homo- and / or - copolymers, cycloolefin-ethylene copolymers, polypropylene homopolymers, statistical propylene copolymers, propylene block copolymers, statistical propylene block copolymers, isotactic polybutene-1 and / or 4-methylpentene 1- homo- and / or copolymers.
  • the polyolefins used for the production of the semi-finished or molded polyolefins can be 0.05 to 2% by mass, based on the polyolefins used, olefin copolymers and acid, acid anhydride and / or epoxy groups / or olefin graft copolymers, preferably ethylene-butyl acrylate-acrylic acid terpolymers with a
  • the charring catalysts of the ammonium polyphosphate and / or zinc borate type contained in the flame retardant compositions cause coking of the aminoplasts, modified aminoplasts and / or C 4 -C 6 polyalcohols contained in the recipes with crust formation, which prevents the polyolefins from dripping in the event of a fire.
  • the aminotriazine blowing agents contained in the flame retardant compositions are preferably melamine, ammeiin, ammelid, melem, melon, melam, benzoguanamine, acetoguanamine, tetramethoxymethylbenzoguanamine, caprinoguanamine and / or butyroguanamine, particularly preferably melamine, and their salts with inorganic and / or organic anions particularly preferably fluorides, chlorides, bromides, iodides, sulfates, phosphates, borates, Silicates, cyanurates, tosylates, formates, acetates, propionates, butyrates and / or maleinates.
  • blowing agents in the flame retardant compositions cause foaming of the flame retardant-containing polyolefin products on the surface when exposed to heat, the thermal conductivity of the polyolefin products being greatly reduced and the flame resistance thereby being increased.
  • the aminoplast-type crust formers contained in the flame retardant compositions are preferably melamine resins, urea resins, ethylene urea resins, cyanamide resins, dicyandiamide resins, guanamine resins, sulfonamide resins, polycarbonylpiperazine resins and / or aniline resins. Melamine resins are particularly preferred.
  • Examples of the melamine resins contained in the flame retardant compositions as crust-forming agents are polycondensates of melamine or melamine derivatives and CrC ⁇ 0 -aldehydes with a molar ratio of melamine or melamine derivative / -C ⁇ -C ⁇ 0 -aldehydes 1: 1 to 1: 6, the melamine derivatives by hydroxy Ci-C-io-alkyl groups, hydroxy-CC-alkyl (oxa-C 2 -C 4 alkyl) ⁇ - 5 groups and / or melamines substituted by amino-CrCi 2 alkyl groups, diaminomethyltriazines and / or diaminophenyltriazines such as 2- (2-HydroxyethylaminoJ ⁇ . ⁇ -diamino-I .S. ⁇ -triazine, 2- (5-hydroxy-3-oxapentylamino) - 4,6-di-amin
  • Caprinoguanamine and or butyroguanamine can be, and wherein the C1-C1 0 - aldehydes are formaldehyde, acetaldehyde, trimethylol acetaldehyde, acrolein, furfural, glyoxal and / or glutaraldehyde, preferably formaldehyde.
  • the C1-C1 0 - aldehydes are formaldehyde, acetaldehyde, trimethylol acetaldehyde, acrolein, furfural, glyoxal and / or glutaraldehyde, preferably formaldehyde.
  • urea-formaldehyde resins mixed condensates with phenols, acid amides or sulfonic acid amides are examples of the urea resins which the flame retardant compositions contain as aminoplasts.
  • guanamine resins contained as flame retardant compositions as aminoplasts are resins which, as guanamine component, benzoguanamine, acetoguanamine, tetramethoxymethylbenzoguanamine,
  • Caprinoguanamine and / or Butyroguanamin contain.
  • sulfonamide resins contained in the flame retardant compositions as aminoplasts are sulfonamide resins made from p-toluenesulfonamide and formaldehyde.
  • aniline resins contained in the flame retardant compositions as aminoplasts are aniline resins which, in addition to aniline, may also contain toluidine and / or xylidines as aromatic diamines.
  • the modified aminoplast-type crust formers contained in the flame retardant compositions are preferably melamine-phenol-formaldehyde mixed condensates, melamine-urea-formaldehyde mixed condensates, melamine resins etherified with dC 8 alcohols and / or C 2 -C 16 polyhydric alcohols, particularly preferably melamine resins etherified with bis (hydroxyethyl) terephthalate, and / or melamine resins modified with copolymers of C 4 -C 2 o-ethylenically unsaturated dicarboxylic acid anhydrides and ethylenically unsaturated monomers, the copolymers of C 4 -C 2 o-ethylenically unsaturated dicarboxylic acid anhydrides and ethylenically unsaturated Monomers preferably partially amidated by reaction with ammonia, CrC 18 monoalkylamines, C 6 -C 8 aromatic monoamines, C 2 -
  • Examples of the melamine resins etherified with C 2 -C 6 polyhydric alcohols in the flame retardant compositions as crust formers are melamine resins which are mixed with ethylene glycol, butylene glycol, octanediol, erythritol, pentites, hexites, heptites monosaccharides and / or esters of aromatic C 8 -C ⁇ 0 - Dicarboxylic acids are etherified with C 2 -C 4 diols.
  • Examples of the melamine resins modified with copolymers of C 4 -C 2 o-ethylenically unsaturated dicarboxylic acid anhydrides and ethylenically unsaturated monomers contained in the flame retardant compositions as crust-forming agents are copolymers of C 4 -C 2o-ethylenically unsaturated acid anhydrides such as maleic anhydride, itaconic dicarboxylic acid anhydride or methyl endonic anhydride Styrene, ⁇ -methylstyrene, ethylene, propylene, isobutene or diisobutene with a molar ratio of 1: 1 to 1: 9 and molar mass weight average of 5000 to 500000, with ammonia, C 8 -C - monoalkylamines such as methylamine or octylamine, C ⁇ -Ci ⁇ -aromatic monoamines such as aniline or naphthylamine, aminotriazines such as mel
  • the crust former of the type C -C 6 polyalcohols contained in the flame retardant compositions are preferably erythritol, pentite, hexite, heptite monosaccharides and / or esters of aromatic C 8 -C 0 dicarboxylic acids with C 2 -C 4 diols. Pentaerythritol and / or bis (hydroxyethyl) terephthalate are particularly preferred.
  • the layered silicates optionally contained in the flame retardant compositions are preferably montmorillonite, bentonite, kaolinite, muscovite, hectorite, fluorhectorite, kanemite, Revdit, grumantite, llerite, saponite, beidelite, nontronite, stevensite, laponite, taneolite, vermiculite, magnesite, volksitoneite, volonsiteite, volonsiteite , Kenyait, Sauconit, Borfluorphlogopite and / or synthetic Smectite, wherein the layer silicates are particularly preferred layer silicates with exchangeable cations of the type alkali, alkaline earth, aluminum, iron and / or manganese cations.
  • Layered silicates are particle diameters from 5 nm to 2000 nm.
  • blowing agents of the triazine type and / or the crust-forming agent of the aminoplast type, modified aminoplasts and / or C 4 -C - ⁇ -polyalcohols can be intercalated into the intermediate layers of the layered silicates by suspending layered silicates in water or mixtures of water in a stirred reactor and dC 8 alcohols with a solids content of 2 to 35% by mass at 20 to 100 ° C.
  • a preferred variant of intercalation of the crust formers of the aminoplast or modified aminoplast type in the intermediate layers of the layered silicates can be carried out by suspending layered silicates in water or mixtures of water and CC 8 alcohols in a stirred reactor with a solids content of 2 to 35 mass% at 20 to 100 ° C and a residence time of 10 to 180 min with solutions or suspensions of aminotriazines in water or mixtures of water and CC 8 alcohols with a solids content of 5 to 90 mass% be homogenized, the mass fraction of the aminotriazines, based on the anhydrous layered silicates, being 20 to 5000% by mass, subsequent to the dispersion of the layered silicates loaded with aminotriazines, optionally after partial separation of the liquid phase, 0.1 to 10% by mass, based on the anhydrous sheet silicates, C Cio-aldehydes as 5 to 50% solutions in water or mixtures of water and d-Cs alcohols, which may be 0.05 to 1, 0
  • Flame retardant compositions are mixtures which consist of a) 55-68% by mass of ammonium polyphosphate, b) 15-20% by mass of melamine intercalated in montmorillonite, which, if necessary after intercalation with formaldehyde at a molar ratio of formaldehyde / melamine of 0.3: 1 to 0, 9: 1 has been implemented, the mass ratio of melamine / montmohlonite being 1: 1 to 1: 3, and c) 15-20% by mass of pentaerythritol, the flame retardant composition in proportions of 24 to 35% by mass in the semi-finished polyolefin and -Form materials with high flame resistance is included.
  • flame retardant compositions consisting of a) 40 to 52 mass% ammonium polyphosphate, b) 25 to 30 mass% melamine, and c) 16 to 25 mass% melamine-formaldehyde resins etherified with bis (hydroxyethyl) terephthalate, the molar ratio melamine / bis ( hydroxyethyl) terephthalate is 1: 1, 0 to 1: 5, with the flame retardant composition being present in proportions of 22 to 35% by mass in the polyolefin semi-finished products and moldings of high flame resistance.
  • a further preferred variant are flame retardant compositions which consist of a) 45 to 55% by mass of ammonium polyphosphate, b) 22 to 30% by mass of melamine and c) 22 to 30% by weight of melamine resin methyl ether with molecular weights of 400 to 3000, the flame retardant composition in proportions of 22 up to 35% by mass is contained in the polyolefin semi-finished products and moldings with high flame resistance.
  • Polyolefin semi-finished products or molding materials containing flame retardant compositions by conventional melt processing methods such as extrusion, injection molding, blow molding or rotary molding can be used in polyolefin / flame retardant mixtures in which the components of the flame retardant composition are tumbled onto the polyolefin granules or powder.
  • a second variant consists in the metering of the flame retardant compositions into the polyolefin melt prior to being shaped into the semi-finished or shaped material. Furthermore, in the production of the polyolefin semifinished products or molded materials containing the flame retardant formulations according to the invention, the flame retardant compositions can be added as a polyolefin masterbatch with a flame retardant content of 40 to 70% by mass by conventional melt processing methods.
  • the flame resistance of the polyolefin flame retardant mixtures was determined using pressed and milled 3mm test specimens by the UL 94 flame test according to CEI IEC 60695-11-10 and the LOI index according to ASTM D 2863-77.
  • the corrosion effect of the polyolefin flame retardant mixtures was determined by melt-kneading the mixtures at 190 ° C./3 min in a laboratory extruder, annealing 1 g of the sample in the platinum crucible, melting the residue on ignition with NaOH, dissolving in water, acidifying with HCI and determining the during Kneading process in the extruder into the polyolefin flame retardant mixture, portions of chromium and nickel characterized by atomic absorption spectroscopy.
  • a mixture of 600 g melamine, 600 g calcium montmorillonite (Südchemie AG, Moosburg, FRG) and 12 l water is heated to 80 ° C. in a 20 l stirred reactor with a bottom drain valve and stirred for 2 hours, the calcium montmorillonite swelling.
  • the modified layered silicate is separated off in a cell filter and dried at 75 ° C./8 hours in a vacuum.
  • the primary particles of the modified calcium montmorillonite have an average particle diameter of 550 nm determined by transmission electron microscopy.
  • the flame retardant composition is prepared by mixing 4 kg of ammonium polyphosphate (FRCros484, Budenheim Iberica), 1 kg of pentaerythritol and 1 kg of the melamine-modified calcium montmorillonite in a tumble mixer for 30 minutes.
  • IJD 44 with side flow dosing for powdery media, decompression zone for vacuum degassing, profile tool 12.7 x 3 mm and extraction device, temperature profile 20/200/200/200/200/200/200/200/200 / 200 ° C, a mixture of a propylene copolymer (melt index 16.0 g / 10 min at 230 ° C / 2.16 kg, ethylene content 4.8 mass%) with 0.10 mass% bis-2.2.6 , 6-tetramethyl-4-piperidyl sebazate and 0.3% by mass, based in each case on the propylene copolymer, of calcium stearate metered at 10.5 kg / h, melted and homogenized.
  • a propylene copolymer melt index 16.0 g / 10 min at 230 ° C / 2.16 kg, ethylene content 4.8 mass
  • the flame retardant composition is metered into the polyolefin melt via a metering device for powdery media in zone 4 at 4.5 kg / h.
  • the mixture is degassed in the decompression zone, discharged as a profile and deducted.
  • Test rods made from the profile 127 x 12.7 x 3 mm showed a fire behavior V-0 in the UL 94 flame test according to CEI IEC 60695-11-10
  • the proportion of chromium in the blend is 5 ppm and the proportion of nickel in the blend is 6 ppm.
  • Flame retardant Exolit 752 AP (based on ammonium polyphosphate / melamine, Clariant) is used in the polyolefin flame retardant mixture in a proportion of 35% by mass, so fire behavior V-0 is also achieved after extrusion of the polypropylene flame retardant mixtures the proportion of chromium in the blend is 19 ppm and the proportion of nickel in the blend is 8 ppm.
  • the primary particles of the polymer-modified montmorillonite have a mean particle diameter of 230 nm determined by transmission electron microscopy.
  • the content of melamine resin in the polymer-modified inorganic particles, determined by elemental analysis and loss on ignition, is 5 / I mass%.
  • the flame retardant composition is prepared by mixing 2 kg of ammonium polyphosphate (FRCros484, Budenheim Iberica), 0.5 kg of pentaerythritol and 0.5 kg of the melamine resin-modified montmorillonite in a tumble mixer for 30 minutes.
  • a Brabender extruder, IJD 42, with side stream dosing for powdery media, decompression zone for vacuum degassing and granulating device, temperature profile 20/180/220/220/220/220/220/220/200/190 ° C, a mixture of a propylene copolymer (melt index 16.0 g / 10 min at 230 ° C / 2.16 kg, ethylene content 4.8 mass%) with 2 mass% maleic anhydride-grafted polypropylene (melt index 28 g / 10 min at 230 ° C / 2.16 kg, maleic anhydride content 0.18 mass%) and 0.5 mass%, each based on the propylene copolymer, metered at 3.0 kg / h of polyethylene wax oxidate, melted and homogenized.
  • the flame retardant formulation is dosed at 3.0 kg / h into zone 4 via a dosing device for powdery media. After intensive homogenization, the mixture is degassed in the decompression zone, discharged and granulated.
  • a granulate mixture of 1.2 kg of flame retardant masterbatch and 0.8 kg of a propylene homopolymer (melt index 25.0 g / 10 min at 230 ° C / 2.16 kg) is placed in a Ferromatic-Millacron injection molding machine FM 60, which is a three-zone screw with a screw length of 22 D, at a melt temperature of 225 ° C and at a mold temperature of 50 ° C according to DIN 16 774 processed to 3 mm standard test bars.
  • the proportion of chromium in the blend is 4 ppm and the proportion of nickel in the blend is 5 ppm.
  • a melamine resin etherified with bis (hydroxyethyl) terephthalate (molar ratio melamine / bis (hydroxyethyl) terephthalate 1: 4) was kneaded at 130 ° by melt-kneading a methanol-etherified melamine-formaldehyde solid resin (molecular weight 1450) with bis (hydroxyethyl) terephthalate C / 10 min.
  • the flame retardant composition is obtained by mixing 4 kg of ammonium polyphosphate (FRCros484, Budenheim Iberica), 1.5 kg of melamine, 0.5 kg of acetoguanamine and 2 kg of the finely ground with bis (hydroxyethyl) terephthalate for 30 minutes etherified melamine resin (molar ratio melamine / bis (hydroxyethyl) terephthalate 1: 4) produced in a tumble mixer.
  • FRCros484, Budenheim Iberica ammonium polyphosphate
  • melamine 0.5 kg of acetoguanamine
  • etherified melamine resin molar ratio melamine / bis (hydroxyethyl) terephthalate 1: 4
  • a propylene copolymer (melt index 16.0 g / 10 min at 230 ° C / 2.16 kg, ethylene content 4.8% by mass) is mixed in the internal mixer with 33% by mass of the flame retardant composition according to 3.1, 0.15% by mass Bis-2 , 2,6,6-tetramethyl-4-piperidyl sebazate and 0.3 mass%, based in each case on the propylene copolymer, of calcium stearate.
  • the proportion of chromium in the blend is 2 ppm and the proportion of nickel in the blend is 3 ppm.
  • the flame retardant composition is obtained by mixing 5 kg of ammonium polyphosphate (FRCros484, Budenheim Iberica), 2.5 kg of melamine and 2.0 kg for 30 minutes Bis (hydroxyethyl) terephthalate and 0.5 kg of methanol-etherified melamine-formaldehyde solid resin (molecular weight 1450) are produced in a tumble mixer.
  • a Brabender extruder, IJD 42, with side stream dosing for powdery media, decompression zone for vacuum degassing and granulating device, temperature profile 20/180/220/220/220/220/220/220/200/190 ° C, a mixture of a propylene copolymer (melt index 16.0 g / 10 min at 230 ° C / 2.16 kg, ethylene content 4.8 mass%) with 2 mass% maleic anhydride-grafted polypropylene (melt index 28 g / 10 min at 230 ° C / 2.16 kg, maleic anhydride content 0.18 mass%) and 0.5 mass%, each based on the propylene copolymer, metered at 3.0 kg / h of polyethylene wax oxidate, melted and homogenized.
  • the flame retardant formulation is then metered into the polyolefin melt via a metering device for powdery media in zone 4 at 3.0 kg / h. After intensive homogenization, the mixture is degassed in the decompression zone, discharged and granulated.
  • a granulate mixture of 1.2 kg of flame retardant masterbatch after 4.1 and 1.2 kg of a propylene homopolymer (melt index 25.0 g / 10 min at 230 ° C./2.16 kg) is in a Ferromatic-Millacron injection molding machine FM 60, the has a three-zone screw with a screw length of 22 D, processed to 3 mm standard test bars at a melt temperature of 225 ° C and at a mold temperature of 50 ° C according to DIN 16 774.
  • the flame retardant composition is mixed for 30 min by mixing 0.50 kg of ammonium polyphosphate (FRCros484, Budenheim Iberica), 0.25 kg of melamine and 0.25 kg of the melamine resin etherified with bis (hydroxyethyl) terephthalate according to 3.1 (molar ratio of melamine / bis (hydroxyethyl) terephthalate 1: 4) made in a tumble mixer.
  • FRCros484, Budenheim Iberica ammonium polyphosphate
  • a Wemer & Pfleiderer extruder, LJD 42, with side flow metering for powdery media, decompression zone for vacuum degassing and granulating device, temperature profile 20/190 / 220/230/230/220/220/220/200 / 190 ° C, a mixture of a polyethylene HD (melt index 15.2 g / 10 min at 190 ° C / 5 kg) with 3 mass% of an ethylene-butyl acrylate-acrylic acid copolymer (melt index 2.5 g 10 min at 190 ° C / 2.16 kg, 5.5 mass% butyl acrylate, 2.1 mass% acrylic acid) and 0.2 mass%, each based on polyethylene, metered at 6.0 kg / h of polyethylene wax oxidate, melted and homogenized.
  • a polyethylene HD melt index 15.2 g / 10 min at 190 ° C / 5 kg
  • the flame retardant composition is then metered into the polyolefin melt via a metering device for powdery media in zone 4 at 2.3 kg / h. After intensive homogenization, the mixture is degassed in the decompression zone, discharged and granulated.
  • the flame retardant-containing polyolefin granulate according to 5.1 is processed in a Ferromatic-Millacron injection molding machine FM 60, which has a three-zone screw with a screw length of 22 D, at a melt temperature of 215 ° C and at a mold temperature of 50 ° C to 3 mm standard test bars.
  • FM 60 Ferromatic-Millacron injection molding machine
  • the standard test rods showed fire behavior V-0 (self-extinguishing, no dripping, no afterglow).
  • the proportion of chromium in the blend is 2 ppm and the proportion of nickel in the blend is 3 ppm.

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Abstract

L'invention concerne des compositions d'agents ignifugeants destinées à des demi-produits et des matières à mouler polyoléfiniques présentant une réfractarité élevée et une corrosivité réduite lors du traitement de fusion des mélanges d'agents ignifugeants polyoléfiniques. Lesdits agents ignifugeants sont composés de mélanges intumescents de a) 45 à 68 % en poids de catalyseurs de carbonisation du type polyphosphates d'ammonium et/ou borates de zinc, b) de 15 à 30 % en poids d'agents moussants du type aminotriazines, et c) 15 à 30 % en poids d'agents d'incrustation du type aminoplastes, aminoplastes modifiés et/ou C4-C16-polyalcools, lesdites compositions d'agents ignifugeants étant contenues à hauteur de 22 à 35 % en poids dans les demi-produits et matières à mouler polyoléfiniques présentant une réfractarité élevée.
PCT/EP2003/006177 2002-06-14 2003-06-12 Compositions d'agents ignifugeants destinees a des demi-produits et des matieres a mouler polyolefiniques WO2003106547A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003242685A AU2003242685A1 (en) 2002-06-14 2003-06-12 Flameproofing agent compositions for polyolefin semifinished products and polyolefin molding materials

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AT9012002A AT411902B (de) 2002-06-14 2002-06-14 Flammschutzmittelzusammensetzungen enthaltende polyolefinerzeugnisse
ATA901/02 2002-06-14

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WO2003106547A2 true WO2003106547A2 (fr) 2003-12-24
WO2003106547A3 WO2003106547A3 (fr) 2004-08-19

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AT500875A1 (de) * 2004-07-23 2006-04-15 Intumex Gmbh Intumeszierende klippprofile für brandschutzeinrichtungen
JP2007297489A (ja) * 2006-04-28 2007-11-15 Cci Corp 層間化合物及び複合材料
GB2448514A (en) * 2007-04-18 2008-10-22 Univ Sheffield Hallam Intumescent formulation
CN101293984B (zh) * 2007-04-28 2010-10-27 中国石油化工股份有限公司 一种膨胀成炭阻燃聚丙烯组合物及其制备方法
CN101956326A (zh) * 2009-12-03 2011-01-26 山东俊富无纺布有限公司 聚丙烯sms复合无纺布及其加工方法
RU2491317C2 (ru) * 2011-09-21 2013-08-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова Огнестойкий нанокомпозит и способ его получения
EP2796492A4 (fr) * 2011-12-21 2015-08-26 Tolsa Sa Procédé d'obtention de structures hiérarchiquement ordonnées de phosphates inorganiques sur des phyllosilicates
CN108587160A (zh) * 2018-05-15 2018-09-28 温州市赢创新材料技术有限公司 一种甲基化防火导电薄膜及其制备方法

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT500875A1 (de) * 2004-07-23 2006-04-15 Intumex Gmbh Intumeszierende klippprofile für brandschutzeinrichtungen
JP2007297489A (ja) * 2006-04-28 2007-11-15 Cci Corp 層間化合物及び複合材料
GB2448514A (en) * 2007-04-18 2008-10-22 Univ Sheffield Hallam Intumescent formulation
GB2448514B (en) * 2007-04-18 2010-11-17 Univ Sheffield Hallam Steel component with intumescent coating
CN101293984B (zh) * 2007-04-28 2010-10-27 中国石油化工股份有限公司 一种膨胀成炭阻燃聚丙烯组合物及其制备方法
CN101956326A (zh) * 2009-12-03 2011-01-26 山东俊富无纺布有限公司 聚丙烯sms复合无纺布及其加工方法
CN101956326B (zh) * 2009-12-03 2014-02-26 山东俊富无纺布有限公司 聚丙烯sms复合无纺布及加工方法
RU2491317C2 (ru) * 2011-09-21 2013-08-27 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова Огнестойкий нанокомпозит и способ его получения
EP2796492A4 (fr) * 2011-12-21 2015-08-26 Tolsa Sa Procédé d'obtention de structures hiérarchiquement ordonnées de phosphates inorganiques sur des phyllosilicates
US9528048B2 (en) 2011-12-21 2016-12-27 Tolsa, S.A. Method for obtaining hierarchically ordered inorganic phosphate structures on phyllosilicates
CN108587160A (zh) * 2018-05-15 2018-09-28 温州市赢创新材料技术有限公司 一种甲基化防火导电薄膜及其制备方法

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AU2003242685A1 (en) 2003-12-31
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AT411902B (de) 2004-07-26
WO2003106547A3 (fr) 2004-08-19

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