HK1202568B - Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof - Google Patents

Description

Flame retardant mixture comprising a flame retardant and aluminum phosphite, method for the production thereof and use thereof

The invention relates to flame retardant mixtures comprising flame retardants and aluminum phosphites, to a process for their preparation and to their use.

Flame retardants are known from the prior art, which are used alone or together with other components (especially synergists) in various types of polymers. These synergists (also known as flame retardant synergists) must not have flame retardant activity per se, but can greatly enhance the efficacy of the flame retardant. Generally, various components such as flame retardants, flame retardant synergists, additives and fillers are mixed with the polymer to be flame-retardant-treated by kneading and extrusion. The process is carried out at temperatures at which the polymer is present in molten form and can significantly exceed 320 ℃ in a short time. All components, especially the flame retardant and the flame retardant synergist, must be able to withstand this temperature in order to maintain their efficacy (i.e. here flame retardant efficacy) and to obtain a flame retardant polymer mixture.

Surprisingly, it has now been found that the combination of the flame retardant of the present invention with aluminum phosphite is significantly more thermally stable than if the flame retardant was used alone or the aluminum phosphite was used alone. The claimed mixtures also exhibit synergistic effects if they act as flame retardants.

Accordingly, the present invention relates to flame retardant mixtures comprising a flame retardant and aluminum phosphite.

Preferably, the flame retardant is a dialkylphosphinic acid and/or a salt thereof; condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with polyphosphoric acid or mixtures thereof; formula (NH)₄)_yH_3-yPO₄Or (NH)₄PO₃)_zWherein y is equal to 1 to 3 and z is equal to 1 to 10,000; benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, dicyandiamide and/or guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate and/or zinc stannate.

Preferably, the dialkylphosphinic acid or salt thereof corresponds to formula (IV)

Wherein

R¹、R²Identical or different and denotes linear or branched C₁-C₆An alkyl group;

m represents Mg, Ca, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H and/or a protonated nitrogen base;

m represents 1 to 4.

Preferably, the flame retardant is also melam, melem, melon, dimelamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate and/or melem polyphosphate and/or mixed poly salts thereof and/or is ammonium hydrogen phosphate, ammonium dihydrogen phosphate and/or ammonium polyphosphate.

Preferably, the flame retardant is also aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, monophenylphosphinic acid and salts thereof, mixtures of dialkylphosphinic acids and salts thereof and monoalkylphosphinic acids and salts thereof, 2-carboxyethylalkylphosphinic acids and salts thereof, 2-carboxyethylmethylphosphinic acids and salts thereof, 2-carboxyethylarylphosphinic acids and salts thereof, 2-carboxyethylphenylphosphinic acids and salts thereof, the adduct of oxa-10-phosphaphenanthrene (DOPO) and salts thereof and p-benzoquinone or itaconic acid and salts thereof.

Preferably, the aluminum phosphite is an aluminum phosphite of formula (I), (II) and/or (III)

Al₂(HPO₃)₃×(H₂O)_q(I)

Wherein

q represents 0 to 4

Al_2.00M_z(HPO₃)_y(OH)_v×(H₂O)_w(II)

Wherein

M represents an alkali metal ion

z represents 0.01 to 1.5

y represents 2.63 to 3.5

v represents 0 to 2 and w represents 0 to 4

Al_2.00(HPO₃)_u(H₂PO₃)_t×(H₂O)_s(III)

Wherein

u represents 2 to 2.99

t represents 2 to 0.01 and

s represents a number of atoms from 0 to 4,

and/or a mixture of aluminium phosphite of formula (I) with a poorly soluble aluminium salt and nitrogen-free impurity ions, a mixture of aluminium phosphite of formula (III) with an aluminium salt, aluminium phosphite [ Al (H)₂PO₃)₃]Aluminum secondary phosphite [ Al ]₂(HPO₃)₃]Basic aluminum phosphite [ Al (OH) (H)₂PO₃)₂ ^*2aq]Aluminum phosphite tetrahydrate [ Al ]₂(HPO₃)₃ ^*4aq]Aluminum phosphonate, Al₇(HPO₃)₉(OH)₆(1, 6-hexanediamine)_1.5 ^*12H₂O、Al₂(HPO₃)^3*×Al₂O₃ ^*nH₂O wherein x is 2.27-1 and/or A_l4H₆P₁₆O₁₈。

Preferably, in the aluminium phosphite of the formula (I)

q represents 0.01 to 0.1.

Preferably, in the aluminum phosphite of the formula (II)

z represents a number of 0.15 to 0.4,

y represents a number of 2.80 to 3,

v represents 0.1 to 4.0 and

w represents 0.01 to 0.1.

Preferably, in the aluminum phosphite of the formula (III)

u denotes 2.834 to 2.99

t represents 0.332 to 0.03 and

s represents 0.01 to 0.1.

The invention also relates to flame retardant mixtures according to one or more of claims 1 to 9, which contain 0.1 to 99.9% by weight of flame retardant and 0.1 to 99.9% by weight of aluminum phosphite of the formula (I), (II) and/or (III) and/or mixtures of aluminum phosphite of the formula (III) with sparingly soluble aluminum salts and nitrogen-free impurity ions and/or mixtures of aluminum phosphite of the formula (III) with aluminum salts.

Preferably, the flame retardant mixture contains 50 to 99.9 wt.% of flame retardant and 0.1 to 50 wt.% of aluminum phosphite of formula (I), (II) and/or (III) and/or a mixture of aluminum phosphite of formula (I) with a poorly soluble aluminum salt and nitrogen-free impurity ions and/or a mixture of aluminum phosphite of formula (III) with an aluminum salt.

The invention also relates to a method for producing flame retardant mixtures according to one or more of claims 1 to 11, characterized in that a powdery flame retardant is mixed with a powdery aluminum phosphite of the formula (I), (II) and/or (III) and/or a mixture of aluminum phosphite of the formula (III) with a sparingly soluble aluminum salt and nitrogen-free impurity ions and/or a mixture of aluminum phosphite of the formula (III) with an aluminum salt.

The invention also relates to the use of the flame retardant mixture according to one or more of claims 1 to 11 as an intermediate product for further synthesis, as a binder, as an accelerator or crosslinker in the curing of epoxy resins, polyurethane and unsaturated polyester resins, as a polymer stabilizer, as a plant protection agent, as a chelating agent, as a mineral oil additive, as an anticorrosion protection agent, in detergent and cleaner applications, in electronic applications.

Preferably, the use of the flame retardant mixture according to one or more of claims 1 to 11 for or as flame retardants, in particular for or as flame retardants for varnishes and foamed coatings, for or as flame retardants for wood and other cellulose-containing products, for or as reactive and/or nonreactive flame retardants for polymers, for the preparation of flame-retardant polymer molding materials, for the preparation of flame-retardant polymer moldings and/or for equipping polyester and cellulose pure and mixed fabrics with flame retardancy by impregnation and/or as synergists in other flame retardant mixtures.

The invention also relates to flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 0.1 to 45% by weight of a flame retardant mixture as claimed in one or more of claims 1 to 11, from 55 to 99.9% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 0 to 55% by weight of additives and from 0 to 55% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

Preferably, the invention relates to flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments and polymer fibers comprising from 1 to 30% by weight of a flame retardant mixture as claimed in one or more of claims 1 to 11, from 10 to 97% by weight of a thermoplastic or thermosetting polymer or mixtures thereof, from 1 to 30% by weight of additives and from 1 to 30% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

Preferably, the plastic of the flame retardant thermoplastic or thermoset polymer molding material, the polymer molding, the polymer film, the polymer filaments and the polymer fibers is a polystyrene HI (high impact) thermoplastic polymer, a polyphenylene ether, a polyamide, a polyester, a polycarbonate and ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/polystyrene-HI) plastic based blend or polymer blend and/or an unsaturated polyester or epoxy resin type thermoset polymer.

Preferably, the mixture of the invention has a particle size of 0.1 to 1000 μm.

Preferably, the mixtures according to the invention have a bulk density of from 80 to 800g/l, particularly preferably from 200 to 700 g/l.

Preferably, the mixtures according to the invention have an L-color of from 85 to 99.9, particularly preferably from 90 to 98.

Preferably, the mixtures according to the invention have an a-color value of from-4 to +9, particularly preferably from-2 to + 6.

Preferably, the mixtures according to the invention have b color values of preferably from-2 to +6, particularly preferably from-1 to + 3.

The color values are given in the System according to Hunter (CIE-LAB-System, Commission International d' Eclairage). L values from 0 (black) to 100 (white), a values from-a (green) to + a (red) and b values from-b (blue) to + b (yellow).

Preferred dialkylphosphinic salts are aluminum tris (diethylphosphinate), aluminum tris (methylethylphosphinate), titanyl bis (diethylphosphinate), titanium tetrakis (diethylphosphinate), titanyl bis (methylethylphosphinate), titanium tetrakis (methylethylphosphinate), zinc bis (diethylphosphinate), zinc bis (methylethylphosphinate), and mixtures thereof.

The mixtures according to the invention in principle also comprise mixtures of one or more flame retardants with one or more aluminum phosphites, i.e. mixtures which can be tripled, quadrupled or more.

Preferred polymer additives for flame-retardant polymer molding materials and flame-retardant polymer moldings are UV absorbers, light stabilizers, lubricants, colorants, antistatic agents, nucleating agents, fillers, reinforcing agents and/or synergists.

Preference is given to the use of the flame-retardant polymer moldings of the invention as lamp components, such as lamp bases and lampholders, plugs and sockets, coil formers, capacitors or contactors, and also housings for safety switches, relay housings and reflectors.

The invention also relates to intumescent flame retardant coatings comprising 1 to 50 wt.% of the flame retardant mixture according to the invention containing flame retardant and aluminum phosphite, 0 to 60 wt.% of ammonium polyphosphate and 0 to 80 wt.% of binders, blowing agents, fillers and/or polymer additives.

In the mixture of aluminum phosphite of formula (I) with a sparingly soluble aluminum salt and nitrogen-free impurity ions, the sparingly soluble aluminum salt is preferably aluminum hydroxide, aluminum hydroxychloride, polyhydroxyaluminum compound, aluminum carbonate, hydrotalcite (Mg)₆Al₂(OH)₁₆CO₃×nH₂O), dihydroxy aluminum sodium carbonate (NaAl (OH)₂CO₃) Aluminum oxides, aluminum oxide hydrates, mixed aluminum hydroxides, basic aluminum sulfate and/or alunite, the impurity ions preferably being chloride, complex chloride and bromide; is hydroxide, peroxide hydrate, sulfite, sulfate, hydrated sulfate, acid sulfate, hydrogen sulfate, persulfate, and peroxodisulfate; is nitrate radical; as carbonate, percarbonate and tinAcid radical; borate, perborate and perborate hydrate; is formate, acetate, propionate, lactate and/or ascorbate, and/or is a cation of the elements Li, Na, K, Mg, Ca, Ba, Pb, Sn, Cu, Zn, La, Ce, Ti, Zr, V, Cr, Mn, Fe, Co and/or Ni.

Preferably, the aluminium salt in the mixture of aluminium phosphite and aluminium salt of formula (III) is aluminium metal, an aluminium alloy, an oxide, a hydroxide, a peroxide hydrate, a carbonate, a percarbonate, a mixed carbonate/hydrate, a formate, an acetate, a propionate, a stearate, a lactate, an ascorbate, an oxalate, or an aluminium salt having an anion of an acid with a higher vapour pressure than phosphorous acid.

Preferably, the polymer is derived from a thermoplastic polymer (such as a polyester, polystyrene or polyamide) and/or a thermoset polymer.

Preferably, the polymer is a polymer of monoolefins and diolefins, such as the polymerization products of polypropylene, polyisobutylene, poly-1-butene, poly-4-methyl-1-pentene, polyisoprene or polybutadiene, and cycloolefins such as cyclopentene or norbornene; also polyethylene (which may optionally be crosslinked), for example High Density Polyethylene (HDPE), high density and high molar mass polyethylene (HDPE-HMW), high density and ultra high molar mass polyethylene (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), branched low density polyethylene (VLDPE), and mixtures thereof.

Preferably, the polymers are copolymers of monoolefins and diolefins with one another or with other vinyl monomers, for example ethylene-propylene copolymers, Linear Low Density Polyethylene (LLDPE) and mixtures thereof with low density polyethylene, propylene-1-butene copolymers, propylene-isobutylene copolymers, ethylene-1-butene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene-acrylic acid copolymers and salts (ionomers) thereof, And terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene, and also mixtures of these copolymers with one another, such as polypropylene/ethylene propylene copolymers, LDPE/ethylene vinyl acetate copolymers, LDPE/ethylene acrylic acid copolymers, LLDPE/ethylene vinyl acetate copolymers, LLDPE/ethylene acrylic acid copolymers and alternating or random polyolefin/carbon monoxide copolymers and mixtures thereof with other polymers, such as polyamides.

Preferably, the polymer is a hydrocarbon resin (e.g., C)₅-C₉) Including hydrogenated modifications thereof (e.g., tackifier resins) and mixtures of polyolefins and starch.

Preferably, the polymer is polystyrene (A), (B), (C), (143e (basf)), poly (p-methylstyrene), poly (α -methylstyrene).

Preferably, the polymer is a copolymer of styrene or alpha-methylstyrene with a diene or an acrylic acid derivative, such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methacrylate; high impact mixtures composed of styrene copolymers and other polymers (for example polyacrylates, diene polymers or ethylene-propylene-diene terpolymers); and styrene block copolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene-styrene, or styrene-ethylene/propylene-styrene).

Preferably, the polymer is a graft copolymer of styrene or alpha-methylstyrene, for example styrene grafted on polybutadiene, styrene grafted on polybutadiene-styrene copolymer or polybutadiene-acrylonitrile copolymer, styrene and acrylonitrile (or methacrylonitrile) grafted on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride grafted on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene, styrene and alkyl acrylate or methacrylate on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof, such as those known, for example, as so-called ABS, MBS, ASA or AES polymers.

Preferably, the styrene polymer is a coarse-cell foam such as EPS (expanded polystyrene), for example styropor (basf) and/or a fine-cell foam such as XPS (extruded polystyrene rigid foam), for example(BASF). Preference is given to polystyrene foams, for exampleXPS、(Dow Chemical)、Styropor、And

preferably, the polymer is a halogen-containing polymer, such as polychloroprene, chlorinated rubbers, chlorinated and brominated isobutylene-isoprene copolymers (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, ethylene and vinyl chloride copolymers, epichlorohydrin homo-and copolymers, especially polymers composed of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and copolymers thereof, such as vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

Preferably, the polymers are polymers derived from α, β -unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polymethyl methacrylates impact-modified with butyl acrylate, polyacrylamides and polyacrylonitriles and copolymers of the mentioned monomers with one another or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

Preferably, the polymer is a polymer derived from unsaturated alcohols and amines and their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and their copolymers with olefins.

Preferably, the polymers are homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with diglycidyl ethers.

Preferably, the polymer is a polyacetal, such as polyoxymethylene, and polyoxymethylenes containing comonomers, such as ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

Preferably, the polymers are polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.

Preferably, the polymer is a polyurethane derived from polyethers, polyesters and polybutadienes having terminal hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

Preferably, the polymers are polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 2/12, polyamide 4 (poly-4-aminobutyric acid,DuPont company), polyamide 4/6 (poly (tetramethylene adipamide),4/6, DuPont corporation), polyamide 6 (polycaprolactam, poly 6-aminocaproic acid,6, DuPont corporation, DuPont,k122, DSM corporation;7301, DuPont corporation;b29, Bayer), polyamide 6/6 ((poly (N, N' -hexamethylene adipamide),6/6,DuPont the company "A" is,101, DuPont corporation;A30,AKV,AM, Bayer corporation;a3, BASF corporation), polyamide 6/9 (poly (hexamethylene nonanoylamide),6/9, DuPont corporation), polyamide 6/10 (poly (hexamethylene sebacamide),6/10 from DuPont corporation), polyamide 6/12 (poly (hexamethylene dodecanediamide),6/12, DuPont corporation), polyamide 6/66 (poly (hexamethylene adipamide-co-caprolactam),6/66, DuPont), polyamide 7 (poly-7-aminoheptanoic acid,7, DuPont), polyamide 7,7 (polyheptaalkylene pimelamide,7,7, DuPont), polyamide 8 (poly-8-aminocaprylic acid,8, DuPont), polyamide 8,8 (poly octaalkyleneoctanediamide,8,8, DuPont), polyamide 9 (poly-9-aminononanoic acid,9, DuPont), polyamide 9,9 (poly nonaalkylene nonanoylamide,9,9, DuPont), polyamide 10 (poly-10-aminodecanoic acid,10, DuPont), polyamide 10,9 (poly (decaalkylene nonanoylamide),10,9, DuPont), polyamide 10,10 (polydecamethylene sebacamide,10,10, DuPont), polyamide 11 (poly-11-aminoundecanoic acid,11, DuPont), polyamide 12 (polydodecalactam,12, a product of DuPont corporation,l20, Ems Chemie corporation), aromatic polyamides derived from meta-xylene, diamines and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid (polyhexamethyleneisophthalamide, polyhexamethyleneterephthalamide) and optionally an elastomer as modifier, for example poly-2, 4, 4-trimethylhexamethyleneterephthalamide or polyisophthaloyl-metaphenylene-diamide. The above polyamide and polyolefinOlefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Polyamides or copolyamides modified also with EPDM or ABS; and polyamides condensed during processing ("RIM-polyamide systems").

Preferably, the polymer is a polyurea, polyimide, polyamideimide, polyetherimide, polyesterimide, Polyhydantoine (Polyhydantoine), and polybenzimidazole.

Preferably the polymer is a polyester derived from dicarboxylic acids and diols and/or hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate,(2500,2002, Celanese corporation;BASF corporation), poly (1, 4-dimethylolcyclohexane terephthalate), polyhydroxybenzoates, and block polyetheresters derived from polyethers having hydroxyl end groups; also polyesters modified with polycarbonates or MBS.

Preferably, the polymers are polycarbonates and polyester carbonates.

Preferably, the polymer is polysulfone, polyethersulfone and polyetherketone.

Preferably, the polymer is a crosslinked polymer derived on the one hand from aldehydes and on the other hand from phenols, ureas or melamines, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.

Preferably, the polymer is a drying and non-drying alkyd resin.

Preferably, the polymer is an unsaturated polyester resin derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols, and also vinyl compounds as crosslinking agents, and also halogen-containing, flame-retardant modifications thereof.

Preferably, the polymer is a crosslinkable acrylic resin derived from a substituted acrylate, for example from an epoxy acrylate, a urethane acrylate or a polyester acrylate.

Preferably, the polymers are alkyd, polyester and acrylate resins, which are crosslinked with melamine, urea, isocyanate, isocyanurate, polyisocyanate or epoxy resins.

Preferably, the polymer is a crosslinked epoxy resin derived from products of aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol-a-diglycidyl ether, bisphenol-F-diglycidyl ether, which are crosslinked with the aid of conventional curing agents, such as anhydrides or ammonia, with or without accelerators.

Preferably, the polymer is a mixture (polymer blend) of the above-mentioned polymers, such as PP/EPDM (polypropylene/ethylene-propylene-diene rubber), polyamide/EPDM or ABS (polyamide/ethylene-propylene-diene rubber or acrylonitrile-butadiene-styrene), PVC/EVA (polyvinyl chloride/ethylene vinyl acetate), PVC/ABS (polyvinyl chloride/acrylonitrile-butadiene-styrene), PVC/MBS (polyvinyl chloride/methacrylate-butadiene-styrene), PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene), PBTP/ABS (polybutylene terephthalate/acrylonitrile-butadiene-styrene), PC/ASA (polycarbonate/acrylate-styrene-acrylonitrile), PC/PBT (polycarbonate/polybutylene terephthalate), PVC/CPE (polyvinyl chloride/chlorinated polyethylene), PVC/acrylates (polyvinyl chloride/acrylate), POM/thermoplastic PUR (polyoxymethylene/thermoplastic polyurethane), PC/thermoplastic PUR (polycarbonate/thermoplastic polyurethane), POM/acrylates (polyoxymethylene/acrylate), POM/MBS (polyoxymethylene/methacrylate-butadiene-styrene), PPO/HIPS (polyphenylene oxide/high impact polystyrene), PPO/PA 6.6 (polyphenylene oxide/polyamide 6.6) and copolymers, PA/HDPE (polyamide/high density polyethylene), PA/PP (polyamide/polyethylene), PA/PPO (polyamide/polyphenylene oxide), PBT/PC/ABS (polybutylene terephthalate/polycarbonate/acrylonitrile-butadiene-styrene) and/PBT/PET/PC (polybutylene terephthalate/polyethylene terephthalate/polycarbonate).

Suitable compounding units which can be used for the preparation of the polymer molding materials are single-shaft extruders or single-screw extruders, for example those from Berstorff GmbH, Hannover and/or Leistritz, N ü rnberg.

Suitable compounding units are also twin-screw extruders, such as those of Coperion Werner & Pfleiderer GmbH & Co. KG, Stuttgart (ZSK 25, ZSK30, ZSK 40, ZSK 58, ZSK MEGAcompouter 40,50,58,70,92,119,177,250,320,350,380) and/or Berstorff GmbH, Hannover, Leistrz extreme GmbH, N ü rnberg.

Also useful are ring slot extruders such as 3+ Extruder GmbH, Laufen, one ring with three to twelve small screws rotating around a static core; and/or planetary gear extruders such as those of Entex corporation, boccum; and/or a vented extruder and/or a tandem extruder and/or a Maillefer-screw.

Suitable compounding units are also compounding machines with twin screws running in opposite directions, for example of the type Compex 37-or-70 from Krauss-Maffei Berstorff.

The effective screw length (L) is 20 to 40D in the case of single-screw or single-screw extruders, for example 25D in the case of multizone screw extruders, where the feed zone (L ═ 10D), transition zone (L ═ 6D), discharge zone (L ═ 9D); and in the case of a twin-screw extruder from 8 to 40D.

Preparation, processing and testing of flame-retardant Plastic Molding materials and Plastic moldings

The flame-retardant component is mixed with the polymer pellets and possible additives and processed on a twin-screw extruder (LeistritzLSM 30/34 type) at temperatures of 230 to 260 ℃ (PBT-GV) or at temperatures of 260 to 280 ℃ (PA 66-GV). The homogenized polymer strand (Polymerstrang) was removed, cooled in a water bath and then pelletized.

After sufficient drying, the molding materials were processed to give test specimens on an injection molding machine (Arburg Allrounder type) at a batch temperature of 240 to 270 ℃ (PBT-GV) or at a batch temperature of 260 to 290 ℃ (PA 66-GV).

The molded bodies composed of the respective mixtures were tested for UL 94(Underwriter laboratories) fire protection rating on test specimens having a thickness of 1.5 mm.

The following fire ratings were derived from UL 94:

v-0 is not more than 10 seconds of afterflame, the total of the afterflame time of 10 times of ignition is not more than 50 seconds, no combustion drips, the sample is not completely burnt out, and no residual incandescence exists in more than 30 seconds after the ignition is finished.

The subsequent burning time after V-1 ignition is finished does not exceed 30 seconds, the total burning time after 10 times of ignition does not exceed 250 seconds, no sample residue is generated after more than 60 seconds after the ignition is finished, and the other standards are the same as those of V-0;

v-2 igniting cotton by burning and dripping, and the other standards are the same as those of V-1;

non-gradeable (nkl): does not satisfy the fire-fighting class V-2.

Testing of thermal stability and phosphine formation

An important criterion for the thermal stability of the aluminium hydrogen phosphites according to the invention is the temperature at which decomposition starts and toxic pH is formed₃. Release of the flame retardant polymer must be avoided when preparing the polymer. For the determination, the material samples were heated in a tube furnace under flowing nitrogen (30l/g) in the following manner: so that the temperature is gradually increased. When adoptingCompany's probe tubes can measure over 1ppm pH₃(for short tubules of phosphine) the decomposition temperature is reached.

Determination of the Water of crystallization content (residual humidity)

The sample was heated in a Muffel oven from Naberterm company heated to 300 ℃ until the weight was constant. This typically lasts 15 minutes. The remaining mass is given based on the initial weighing, calculated as a percentage and the weight loss is subtracted from 100.

The invention is further illustrated by the following examples.

EXAMPLE 1 aluminium sulfite of formula (I)

573g of aluminum hydroxide, 1284g of 70% by weight phosphorous acid, 307g of 25% by weight sulfuric acid and 9,400g of completely desalted water are placed in a 16l high-pressure stirred vessel, heated to 150 ℃ and stirred for 2.5 h. The resulting suspension was drained, filtered at 80 ℃ and washed several times with fully desalted water, then dried at 220 ℃. The aluminum phosphite of formula (I) is obtained in very high (99%) yield with very high thermal stability (PH)₃Formation starts from 360 ℃).

EXAMPLE 2 aluminum sulfite of formula (I)

593g of aluminum hydroxide, 1330g of 70% by weight of phosphorous acid, 318g of 25% by weight of sulfuric acid and 9 l of completely desalted water are initially introduced as in example 1, heated to 145 ℃ and stirred for 3h, then 605g of 25% by weight sodium hydroxide solution are added and stirred for 1.5 h. The suspension was drained, filtered, washed and dried as in example 1. The aluminum phosphite of the formula (I) is obtained in very high yields (99%), with very high thermal stability (PH)₃Formation starts from 380 ℃).

EXAMPLE 3 aluminum sulfite of formula (II)

2958g of water are placed in a 16l high-pressure stirred vessel and heatedBrought to 155 ℃ and stirred. 3362g of aluminum sulfate solution and 2780g of sodium phosphite solution were metered in simultaneously during 3 h. The suspension was drained and filtered at 80 ℃, washed with hot water, redispersed and washed again. The filter cake was dried in a reactor-thermal dryer (Reaktrotherm-Trokner) at 220 ℃. The alkali metal-aluminum-mixed phosphites according to the invention are obtained in very high yields and have a very high thermal stability (pH)₃Formation starts from 380 ℃).

Example 4 aluminum sulfite of formula (II)

Analogously to example 3, water was initially charged at 155 ℃ and the aluminum sulfate solution and the sodium phosphite solution were metered in over 0.5 h. The yield was 85% and the product was thermostable (pH)₃Formation starts from 360 ℃) is very high.

EXAMPLE 5 aluminum phosphite of formula (III)

1644g of aluminum hydroxide (A)710; ALCOA Inc.; 99.6%) were placed in a kneader. 2635g of phosphorous acid (98%) was added thereto in portions under stirring. The reaction started automatically while being exothermic. The reaction was continued at 145 ℃ for 5 h. The composition Al was obtained in a yield of 99.5%₂(HPO₃)_2.89(H₂PO₃)_0.22Aluminum hydrogen phosphite. Very high thermal stability (pH)₃Formation starts from 360 ℃).

EXAMPLE 6 aluminum phosphite of formula (III)

1537g of aluminum hydroxide are reacted with 2463g of phosphorous acid as in example 5. The product contained a composition of Al₂(HPO₃)₂(H₂PO₃)₂And 0.45 weight percent phosphorous acid. The yield is90.5 percent. Very high thermal stability (pH)₃Formation starts from 360 ℃).

Example 7 mixture of aluminum phosphite of formula (III) and aluminum salt

1600g of aluminum hydroxide (710; ALCOA Inc.; 99.6%) were placed in a kneader. To this was added 2570g of phosphorous acid (98%) in portions with mixing. The reaction started automatically while being exothermic. The reaction was continued at 148 ℃ for 160 minutes. The product contained 98.1% by weight of Al in the composition₂(HPO₃)_2.89(H₂PO₃)_0.22Aluminum phosphite, 1.5 weight percent aluminum hydroxide, and 0.25 weight percent unreacted phosphorous acid.

Example 8 mixture of aluminum phosphite of formula (III) and aluminum salt

1600g of aluminum hydroxide and 2570g of phosphorous acid were reacted as in example 7. The product contained 90.8% by weight of Al in the composition₂(HPO₃)₂(H₂PO₃)₂Aluminum phosphite, 8.7 weight percent aluminum hydroxide, and 0.4 weight percent phosphorous acid.

Example 9 mixture of aluminum phosphite of formula (I) with sparingly soluble aluminum salt and nitrogen-free impurity ions

606g of aluminum hydroxide, 1360g of 70% by weight of phosphorous acid, 325g of 25% by weight of sulfuric acid and 10 l of completely desalted water are placed in a 16l high-pressure stirred vessel from Pfaudler, Inc., heated to 155 ℃ and stirred for 170 minutes. The resulting suspension was drained and filtered at 80 ℃ by means of a Seitz pressure filter and washed several times with fully deionized water and redispersed. Then dried at 150 ℃. The formula (II) according to the invention is obtained in very high yields (99%)With a mixture of sparingly soluble aluminum salts (1.3% by weight of aluminum hydroxide) and nitrogen-free impurity ions (0.1% by weight of sulfate), which have a very high thermal stability (pH)₃Formation starts from 360 ℃).

EXAMPLE 10 mixture of aluminium phosphite of formula (I) with a sparingly soluble aluminium salt and nitrogen-free impurity ions

634g of aluminum hydroxide, 1420g of 70% by weight phosphorous acid, 340g of 25% by weight sulfuric acid and 10 l of completely desalted water are initially charged as in example 9, heated to 125 ℃ and stirred for 3h, and then 646g of 25% by weight sodium hydroxide solution are added and stirred for 80 minutes. The suspension was drained, filtered, washed and dried as in example 9. The inventive mixture of aluminum phosphite of the formula (III) with a sparingly soluble aluminum salt (3% by weight of aluminum hydroxide) and nitrogen-free impurity ions (0.3% by weight of sodium, 0.1% by weight of sulfate) is obtained in very high yields (98.9%), with very high thermal stability (pH)₃Formation starts from 380 ℃).

Example 11 (comparative)

Commercially available aluminum phosphites, which are not according to the invention, exhibit a lower thermal stability (pH) than the aluminum phosphites₃Formation starts from 320 ℃).

Example 12 aluminum phosphite of formula (I) in Polyamide

52% by weight of polyamide 66 polymer, 28% by weight of glass fibers, 3.9% by weight of phosphite according to example 1 and 16.1% by weight of aluminum diethylphosphinateOP1230(Clariant corporation) produced a flame-retardant polymer molding in the form of a UL-94 test specimen rod and a flame-retardant polymer molding material according to the general procedure described. UL-94 testYielding a V-0 rating.

Example 13 aluminum phosphite of formula (I) in polyester

52% by weight of polybutylene terephthalate polymer, 28% by weight of glass fibers, 3.9% by weight of aluminum phosphite according to example 1 and 16.1% by weight of aluminum diethylphosphinate were usedOP1240 (Clariant) the flame-retardant polymer moldings and flame-retardant polymer molding materials in the form of UL-94 test specimen bars were produced according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 14 aluminum phosphite of formula (II) in Polyamide

52% by weight of a polyamide 66 polymer, 28% by weight of glass fibers, 3.9% by weight of aluminum phosphite according to example 3 and 16.1% by weight of aluminum diethylphosphinateOP1230(Clariant corporation) produced a flame-retardant polymer molding in the form of a UL-94 test specimen rod and a flame-retardant polymer molding material according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 15 aluminum phosphite of formula (II) in polyester

52% by weight of polybutylene terephthalate polymer, 28% by weight of glass fibers, 3.9% by weight of aluminum phosphite according to example 3 and 16.1% by weight of aluminum diethylphosphinate were usedOP1240(Clariant Corp.) A flame-retardant polymer molded body in the form of a UL-94 test specimen rod and a flame-retardant polymer were produced according to the general procedure describedAnd (3) molding the material. The UL-94 test gives a V-0 rating.

Example 16 aluminum phosphite of formula (III) in Polyamide

52% by weight of a polyamide 66 polymer, 28% by weight of glass fibers, 3.9% by weight of aluminum phosphite according to example 5 and 16.1% by weight of aluminum diethylphosphinate were usedOP1230(Clariant corporation) produced a flame-retardant polymer molding in the form of a UL-94 test specimen rod and a flame-retardant polymer molding material according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 17 aluminum phosphite of formula (II) in polyester

52% by weight of polybutylene terephthalate polymer, 28% by weight of glass fibers, 3.9% by weight of aluminum phosphite according to example 5 and 16.1% by weight of aluminum diethylphosphinate were usedOP1240 (Clariant) the flame-retardant polymer moldings and flame-retardant polymer molding materials in the form of UL-94 test specimen bars were produced according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 18 mixture of aluminum salt in Polyamide and aluminum hydrogenphosphite of formula (III)

52% by weight of a polyamide 66 polymer, 28% by weight of glass fibers, 3.9% by weight of a mixture of aluminum salt according to example 7 and aluminum hydrogenphosphite of the formula (III) and 16.1% by weight of aluminum diethylphosphinateOP1230(Clariant Corp.) As stated in generalThe procedure produces flame-retardant polymer moldings and flame-retardant polymer molding materials in the form of UL-94 test specimen bars. The UL-94 test gives a V-0 rating.

Example 19 mixture of aluminum salt in polyester and aluminum hydrogenphosphite of formula (III)

52% by weight of polybutylene terephthalate polymer, 28% by weight of glass fibers, 3.9% by weight of a mixture of aluminum salt according to example 7 and aluminum hydrogenphosphite of the formula (III) and 16.1% by weight of aluminum diethylphosphinateOP1240 (Clariant) the flame-retardant polymer moldings and flame-retardant polymer molding materials in the form of UL-94 test specimen bars were produced according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 20

52% by weight of a polyamide 66 polymer, 28% by weight of glass fibers, 3.9% by weight of a mixture of aluminum phosphite of the formula (I) according to example 9 with sparingly soluble aluminum salts and nitrogen-free impurity ions, and 16.1% by weight of aluminum diethylphosphinateOP1230(Clariant corporation) produced a flame-retardant polymer molding in the form of a UL-94 test specimen rod and a flame-retardant polymer molding material according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 21

52% by weight of polybutylene terephthalate polymer, 28% by weight of glass fibers, 3.9% by weight of a mixture of aluminum phosphite of the formula (I) according to example 10 with sparingly soluble aluminum salts and nitrogen-free impurity ions, and 16.1% by weight of aluminum diethylphosphinateOP1240 (Clariant) the flame-retardant polymer moldings and flame-retardant polymer molding materials in the form of UL-94 test specimen bars were produced according to the general procedure described. The UL-94 test gives a V-0 rating.

Example 22 (comparative)

52% by weight of polybutylene terephthalate polymer, 28% by weight of glass fibers, 3.9% by weight of aluminum phosphite from example 11 and 16.1% by weight of aluminum diethylphosphinate were usedOP1240 (Clariant) makes it impossible to process flame-retardant polymer moldings and flame-retardant polymer molding materials in the form of UL-94 test specimen bars by means of the formation of toxic phosphine.

Claims (17)

1. Flame retardant mixture comprising a flame retardant and aluminum phosphite, wherein the aluminum phosphite is an aluminum phosphite of formula (II) and/or (III)

Al_2.00M_z(HPO₃)_y(OH)_v×(H₂O)_w(II)

Wherein

M represents an alkali metal ion

z represents 0.01 to 1.5

y represents 2.63 to 3.5

v represents 0 to 2 and

w represents 0 to 4

Al_2.00(HPO₃)_u(H₂PO₃)_t×(H₂O)_s(III)

Wherein

u represents 2 to 2.99

t represents 2 to 0.01 and

s represents a number of atoms from 0 to 4,

and/or a mixture of aluminium phosphite of formula (I) with a sparingly soluble aluminium salt and nitrogen-free impurity ions, a mixture of aluminium phosphite of formula (III) with an aluminium salt,

Al₂(HPO₃)₃×(H₂O)_q(I)

wherein

q represents 0 to 4.

2. Flame-retardant mixture according to claim 1, characterized in that the flame retardant is a dialkylphosphinic acid and/or salts thereof; condensation products of melamine and/or reaction products of melamine with phosphoric acid and/or reaction products of condensation products of melamine with polyphosphoric acid or mixtures thereof; formula (NH)₄)_yH_3-yPO₄Or (NH)₄PO₃)_zWherein y is equal to 1 to 3 and z is equal to 1 to 10,000; benzoguanamine, tris (hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine cyanurate, dicyandiamide and/or guanidine; magnesium oxide, calcium oxide, aluminum oxide, zinc oxide, manganese oxide, tin oxide, aluminum hydroxide, boehmite, dihydrotalcite, hydrocalumite, magnesium hydroxide, calcium hydroxide, zinc hydroxide, tin oxide hydrate, manganese hydroxide, zinc borate, basic zinc silicate and/or zinc stannate.

3. Flame-retardant mixture according to claim 2, characterized in that the dialkylphosphinic acids or salts thereof correspond to the formula (IV)

Wherein

R¹、R²Identical or different and denotes linear or branched C₁-C₆An alkyl group;

m represents Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, H and/or a protonated nitrogen base;

m represents 1 to 4.

4. Flame retardant mixture according to claim 1, characterized in that the flame retardant is melam, melem, melon, di (melamine) pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate and/or melem polyphosphate and/or mixed poly salts thereof and/or is ammonium hydrogen phosphate, ammonium dihydrogen phosphate and/or ammonium polyphosphate.

5. Flame retardant mixture according to claim 1, characterized in that the flame retardant is aluminum hypophosphite, zinc hypophosphite, calcium hypophosphite, sodium phosphite, monophenylphosphinic acid and its salts, mixtures of dialkylphosphinic acids and their salts with monoalkylphosphinic acids and their salts, 2-carboxyethyl alkylphosphinic acids and their salts, 2-carboxyethyl methylphosphinic acids and their salts, 2-carboxyethyl arylphosphinic acids and their salts, 2-carboxyethyl phenylphosphinic acids and their salts, the adduct of oxa-10-phosphaphenanthrene (DOPO) and its salts with p-benzoquinone or itaconic acid and its salts.

6. Flame retardant mixture according to any of claims 1 to 5, characterized in that q represents 0.01 to 0.1 in the aluminium phosphite of formula (I).

7. Flame retardant mixture according to any of claims 1 to 5, characterized in that in the aluminum phosphite of the formula (II) z represents 0.15 to 0.4, y represents 2.80 to 3, v represents 0.1 to 4.0 and w represents 0.01 to 0.1.

8. Flame retardant mixture according to any of claims 1 to 5, characterized in that in the aluminum phosphite of the formula (III) u represents 2.834 to 2.99, t represents 0.332 to 0.03 and s represents 0.01 to 0.1.

9. Flame retardant mixture according to any of claims 1-5, containing 0.1 to 99.9 wt.% of flame retardant and 0.1 to 99.9 wt.% of aluminum phosphites of the formula (II) and/or (III) and/or mixtures of aluminum phosphites of the formula (I) with poorly soluble aluminum salts and nitrogen-free impurity ions and/or mixtures of aluminum phosphites of the formula (III) with aluminum salts.

10. Flame retardant mixture according to any of claims 1-5, containing 50 to 99.9 wt.% of flame retardant and 0.1 to 50 wt.% of aluminum phosphites of the formula (II) and/or (III) and/or mixtures of aluminum phosphites of the formula (I) with poorly soluble aluminum salts and nitrogen-free impurity ions and/or mixtures of aluminum phosphites of the formula (III) with aluminum salts.

11. Process for the preparation of flame retardant mixtures according to any of claims 1 to 10, characterized in that a powdered flame retardant is mixed with a powdered aluminum phosphite of the formula (II) and/or (III) and/or a mixture of aluminum phosphite of the formula (I) with a poorly soluble aluminum salt and nitrogen-free impurity ions and/or a mixture of aluminum phosphite of the formula (III) with an aluminum salt.

12. Use of the flame retardant mixture according to any of claims 1 to 10 as an intermediate product for further synthesis, as a binder, as an accelerator or crosslinker in the curing of epoxy resins, polyurethane and unsaturated polyester resins, as a polymer stabilizer, as a plant protection agent, as a chelating agent, as a mineral oil additive, as an anticorrosion protection agent, in detergent and cleaner applications, in electronic applications.

13. Use of a flame retardant mixture according to any of claims 1 to 10, in or as a flame retardant and/or as a synergist.

14. Use of the flame retardant mixture according to any of claims 1 to 10 for or as flame retardants for varnishes and foamed coatings, for or as flame retardants for wood and other cellulose-containing products, for or as reactive and/or nonreactive flame retardants for polymers, for the preparation of flame-retardant polymer molding materials, for the preparation of flame-retardant polymer moldings and/or for equipping polyester and cellulose pure and mixed fabrics with flame retardancy by impregnation and/or as synergists in other flame retardant mixtures.

15. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments or polymer fibers comprising from 0.1 to 45% by weight of a flame retardant mixture as claimed in any of claims 1 to 10, from 55 to 99.9% by weight of a thermoplastic or thermosetting polymer or mixtures thereof, from 0 to 55% by weight of additives and from 0 to 55% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

16. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments or polymer fibers comprising from 1 to 30% by weight of a flame retardant mixture as claimed in any of claims 1 to 10, from 10 to 97% by weight of a thermoplastic or thermosetting polymer or a mixture thereof, from 1 to 30% by weight of additives and from 1 to 30% by weight of fillers or reinforcing materials, where the sum of the components is 100% by weight.

17. Flame-retardant thermoplastic or thermosetting polymer molding materials, polymer moldings, polymer films, polymer filaments or polymer fibers, which comprises a flame-retardant mixture according to any of claims 1 to 10, characterised in that the plastic of the flame-retardant thermoplastic or thermosetting polymer moulding material, polymer moulded body, polymer film, polymer filament or polymer fibre is a polystyrene HI-type (high impact) thermoplastic polymer, polyphenylene ether, polyamide, polyester, polycarbonate and ABS (acrylonitrile-butadiene-styrene) or PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) or PPE/HIPS (polyphenylene ether/polystyrene-HI) plastic-based blend or polymer blend and/or an unsaturated polyester or epoxy resin-type thermosetting polymer.