Classifications

• • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
  • C08K5/34928—Salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—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
  • 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
  • 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
  • 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
  • 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
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/02—Organic and inorganic ingredients
• • 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 novel acting combinations of
• Flammschutzstoffschsynergisten known and commercially available. Due to the more favorable fire side effects with respect to smoke gas density and flue gas composition, as well as for ecological reasons, non-halogenated flame retardant systems have been used for some time.
• non-halogenated flame retardants the salts of phosphinic acids (phosphinates) have proven particularly effective for thermoplastic polymers (DE 2 252 258 A and DE 2 447 727 A).
• phosphinates the salts of phosphinic acids
• thermoplastic polymers DE 2 252 258 A and DE 2 447 727 A.
• synergistic combinations of phosphinates with certain nitrogen-containing compounds, in particular with melamine derivatives are known which act more effectively in a whole series of polymers as flame retardants than the phosphinates alone (WO-2002/28953 A1 and DE 197 34 437 A1 and DE 197 37 727 A1).
• synergistic combinations of phosphinates with melamine cyanurate are known, which also act more effectively as flame retardants in many polymers than the phosphinates alone (DE 196 14 424 A1 and DE 103 31 889 A1). It is known from US Pat. No. 7,420,007 B2 that dialkylphosphinates containing a small amount of selected telomers are outstandingly suitable
• Flame retardants are suitable for polymers, wherein the polymer is subject to the incorporation of the flame retardant in the polymer matrix only a small degradation.
• Flame retardant additives for polymers described in addition to Mg, Ca, Al, Zn or Fe salts of dialkylphosphinates up to 20 wt .-% of Mg, Ca, Al, Zn or Fe salts of alkyl phosphinates and optionally small amounts of Mg, Ca, Al, Zn or Fe salts of the phosphonic acid. These additives cause in polymer molding compositions a very good flame retardant and a reduction in the corrosion of extruder components in the processing of the molding compositions.
• WO 2006/027340 A1 and WO 2000/002869 A1 disclose polyphosphate derivatives of 1,3,5-triazine compounds which can be used as
• Flame retardants for polymer molding compounds are suitable.
• antioxidants and stabilizers used so that the plastic survives the processing without chemical damage and then for a long time against external influences such as heat
• UV light, weather and oxygen (air) is stable.
• lubricants prevent too much sticking
• Plastics are processed during processing in the melt.
• Flame retardants must often be added in high dosages in order to ensure a sufficient flame retardancy of the plastic according to international standards. Due to their chemical reactivity, which for the
• Flame retardants affect the processing stability of plastics. For example, increased polymer degradation, crosslinking reactions, outgassing or discoloration may occur.
• Glow wire resistance is known, which in addition to phosphinates nitrogen-containing
• Synergists contain as flame retardants.
• Flammschutzstoffysteme with the property profile described above to provide, ie that the invention phosphinat inconveniencen Flammschutzstoffysteme good electrical values (GWFI, CTI) and effective flame retardancy characterized by the shortest possible afterburning. (UL-94, post-combustion time / time).
• the invention therefore relates to containing flame retardant combinations
• Phosphinic acid salt of the formula (I) as component A Phosphinic acid salt of the formula (I) as component A.
• Ri and R2 are ethyl
• M is Al, Fe, TiOp or Zn
• m 2 to ⁇ 4 means, and
• R 3 is ethyl
• Met is Al, Fe, TiOq or Zn
• n 2 to ⁇ 4, preferably 2 or 3
• 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 flame retardant combinations according to the invention are those whose X-ray diffractogram contains the following reflections: in the angular range 2 ⁇ of 9.099 ° to 9.442 °, of 14.765 ° to 15.076 °, of 18.619 ° to 18.984 ° and of 26.268 ° to 26.679 °.
• the proportion of component A is usually 5 to 85 wt .-%, preferably 10 to 60 wt .-%.
• the proportion of component B is usually 0.01 to 10 wt .-%, preferably 0.1 to 2.5 wt .-%.
• the proportion of component C is usually 0.01 to 10 wt .-%, preferably 0.1 to 2.5 wt .-%.
• the proportion of component D is usually 5 to 50 wt .-%, preferably 10 to 30 wt .-%.
• the percentages for the proportions of components A to D relate to the total amount of the flame retardant combinations.
• the proportion of component A is 5 to 85% by weight
• the proportion of component B is from 0.01 to 10% by weight
• the proportion of component D is from 5 to 50% by weight
• the proportion of component A is from 10 to 60% by weight
• the proportion of component B is from 0.1 to 2.5% by weight
• the proportion of component C is from 0.1 to 2.5% by weight
• the proportion of component D is from 10 to 30% by weight
• Preferred salts of component A are those in which M m + Zn 2+ , Fe 3+ or in particular Al 3+ .
• Preferably used salts of component B are zinc, iron or
• salts of component C are those in which Met n + Zn 2+ , Fe 3+ or in particular Al 3+ .
• Component B are present as aluminum salts.
• Diethylphosphoric acid are known flame retardants for polymeric molding compositions. Salts of diethylphosphinic acid with fractions of the phosphinic and phosphonic acid salts used according to the invention as components B and C are known flame retardants. The preparation of this combination of substances is z. B. in US 7,420,007 B2 described.
• Component A may contain small amounts of salts of component B and of salts of component C, for example up to 10% by weight
• Component B preferably 0.01 to 6 wt.%, And in particular 0.2 to 2.5 wt.% Thereof, and up to 10 wt.% Of component C, preferably 0.01 to 6 wt. and in particular from 0.2 to 2.5% by weight thereof, based on the amount of components A, B and C.
• component C preferably 0.01 to 6 wt. and in particular from 0.2 to 2.5% by weight thereof, based on the amount of components A, B and C.
• Ethylphosphonic acid are as additives to diethylphosphinates in
• Flame retardants for polymeric molding compositions also known, for example from WO 2016/065971 A1.
• the use of the polyphosphate derivatives of melamine according to the invention as component D with a degree of condensation of greater than or equal to 20 as flame retardants is also known.
• DE 10 2005 016 195 A1 discloses a stabilized flame retardant containing 99 to 1% by weight.
• Phosphinic acid and / or a phosphinic acid salt can be combined.
• Preferred flame retardant combinations according to the invention comprise as component D a melamine polyphosphate whose average
• Condensation degree 20 to 200 in particular from 40 to 150, is.
• the average is
• Further preferred flame retardant combinations according to the invention contain as component D a melamine polyphosphate which has a
• Decomposition temperature of greater than or equal to 320 ° C, in particular greater than or equal to 360 ° C and most preferably greater than or equal to 400 ° C.
• melamine polyphosphates which are known from WO 2006/027340 A1 (corresponding to EP 1 789 475 B1) and WO 2000/002869 A1 (corresponding to EP 1 095 030 B1).
• melamine polyphosphates whose mean condensation ridge (number average) is> 20 whose decomposition temperature is greater than 320 ° C., the molar ratio of 1,3,5-triazine compound to phosphorus being less than 1, 1, in particular 0.8 to 1, Is 0 and the pH of a 10% slurry in water at 25 ° C is 5 or higher, preferably 5.1 to 6.9.
• components A, B, C and D are in particulate form, the average particle size (dso) being 1 to 100 ⁇ m.
• average particle size 1 to 100 ⁇ m.
• the inorganic phosphonate (component E) preferably corresponds to the general formula (IV) or (V)
• Kat is a p-valent cation, in particular a cation of an alkali metal, alkaline earth metal, an ammonium cation and / or a cation of Fe, Zn or particular AI including the cation AI ( OH) or Al (OH) 2, and p is 1, 2, 3 or 4.
• the inorganic phosphonate (component E) 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 E) 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 to Al7 (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.
• component E is a
• Reaction product of phosphorous acid and an aluminum compound Reaction product of phosphorous acid and an aluminum compound.
• Particularly preferred components E 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)
• Ammonium phosphite alkali phosphites or alkaline earth phosphites.
• Preferred Alkaliphosphite are disodium phosphite, Dinathumphosphithydrat, 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.
• Me is Fe, TiOr, Zn or in particular Al,
• o is 2 to ⁇ 4, 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 E is preferably in an amount of 0.01 to 10 wt .-%, in particular in an amount of 0.1 to 2.5 wt .-%, based on the
• the invention also relates to the use of the invention
• thermoplastic and thermosetting polymers as well as with these
• thermoplastic and / or thermosetting polymers which contain the flame retardant combinations according to the invention and optionally fillers and reinforcing agents and / or other additives as defined below are referred to below as polymer compositions.
• component F Thermoplastic and / or thermosetting polymers which contain the flame retardant combinations according to the invention and optionally fillers and reinforcing agents and / or other additives as defined below are referred to below as polymer compositions.
• Flame retardant combinations can be effectively used, it is amorphous thermoplastic polymers or semi-crystalline
• thermoplastic polymers having a melting point of less than or equal to 290 ° C, preferably less than or equal to 280 ° C, and most preferably less than or equal to 250 ° C. Such polymers have already been described in detail in the literature and are known to the person skilled in the art.
• thermoplastic polymers used according to the invention are determined by means of differential scanning caloimetry (DSC) at a heating rate of 10 K / second.
• thermoplastic polymers used according to the invention include, for example Polymers of mono- and diolefins, for example polypropylene,
• Cyclopentene or norbornene also polyethylene, which is
• High density polyethylene high density polyethylene (HDPE), high density polyethylene (HDPE-HMW), high density polyethylene and ultrahigh molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene Density (LLDPE), branched low density polyethylene (VLDPE).
• HDPE high density polyethylene
• HDPE-HMW high density polyethylene
• HDPE-UHMW medium density polyethylene
• MDPE low density polyethylene
• LDPE low density polyethylene
• LLDPE linear low density polyethylene Density
• VLDPE branched low density polyethylene
• Mixtures of the aforementioned polymers for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (eg.
• PP / HDPE PP / LDP
• blends of various types of polyethylene such as LDPE / HDPE.
• Copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as.
• Low density polyethylene and blends thereof with low density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, etc.
• LDPE / ethylene-acrylic acid copolymers LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers, and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such.
• Acrylic derivatives such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile methacrylate; Blends of high impact strength of styrene copolymers and another polymer, such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; as well as block copolymers of styrene such.
• Styrene-butadiene-styrene styrene-isoprene-styrene
• styrene-ethylene / butylene-styrene styrene-ethylene / propylene-styrene.
• Graft copolymers of styrene or alpha-methylstyrene such as.
• Styrene on polybutadiene styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and
• Polymers such as. B. known as so-called ABS, MBS, ASA or AES polymers.
• Halogen-containing polymers such as. As polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene
• Halobutyl rubber chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Epichlorhydrinhomo- and copolymers, especially polymers of halogen-containing polyethylene
• Vinyl compounds such as. As polyvinyl chloride, polyvinylidene chloride, Polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as
• Vinyl chloride-vinylidene chloride vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.
• Derive derivatives such as polyacrylates and polymethacrylates, with butyl acrylate impact-modified polymethyl methacrylates, polyacrylamides and polyacrylonitriles.
• Copolymers of the monomers mentioned under 8 with each other or with other unsaturated monomers such as.
• acrylonitrile-butadiene copolymers acrylonitrile-alkyl acrylate copolymers, acrylonitrile alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
• Polyacetals such as polyoxymethylene, as well as those polyoxymethylenes, the comonomers, such as. B. contain ethylene oxide; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• Polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides are examples of polyphenylene oxides and sulfides and mixtures thereof with styrene polymers or polyamides.
• Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12 / 12, polyamide 1 1, polyamide 12; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers, or chemically bound or grafted elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or
• IM polyamide systems condensed polyamides
• hydroxycarboxylic acids or the corresponding lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1, 4-dimethylolcyclohexanterephthalat, and block polyether esters derived from polyethers having hydroxyl end groups; also with polycarbonates or MBS modified polyester.
• mixtures (polyblends) of the aforementioned polymers such as. PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate,
• thermosetting polymers in which the inventive thermosetting polymers are thermosetting thermosetting polymers in which the inventive thermosetting polymers
• thermosetting polymers are preferably unsaturated polyester resins (UP resins) which are more saturated and more stable to copolyesters derived unsaturated dicarboxylic acids or their anhydrides with polyhydric alcohols, and vinyl compounds as crosslinking agents.
• UP resins are cured by free-radical polymerization with initiators (eg peroxides) and accelerators.
• Preferred unsaturated dicarboxylic acids and derivatives for the preparation of the UP resins are maleic anhydride and fumaric acid.
• Preferred saturated dicarboxylic acids are phthalic acid, isophthalic acid,
• Terephthalic acid Terephthalic acid, tetrahydrophthalic acid, adipic acid.
• Preferred diols are 1, 2 propanediol, ethylene glycol, diethylene glycol and
• Preferred vinyl compound for crosslinking is styrene.
• Preferred hardener systems are peroxides and metal co-initiators, e.g. B.
• Preferred hydroperoxides are di-tert-butyl peroxide, tert-butyl peroctoate, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl permalate, tert-butyl perisobutyrate, benzoyl peroxide, diacetyl peroxide, succinyl peroxide, p-chlorobenzoyl peroxide and dicyclohexyl peroxide dicarbonate ,
• Preferred metal co-initiators are cobalt, manganese, iron, vanadium, nickel or lead compounds.
• Preferred aromatic amines are dimethylaniline, dimethyl-p-toluene, diethylaniline and phenyldiethanolamine.
• thermosetting polymers are epoxy resins which are aliphatic, cycloaliphatic, heterocyclic or aromatic Derive glycidyl compounds, for. B. of bisphenol A diglycidyl ethers and
• Suitable glycidyl compounds are bisphenol A diglycidyl esters, bisphenol F diglycidyl esters, polyglycidyl esters of phenol formaldehyde resins and cresol formaldehyde resins, polyglycidyl esters of pthalthalene, isophthalic and
• Suitable hardeners are aliphatic, cycloaliphatic, aromatic and
• heterocyclic amines or polyamines such as ethylenediamine, diethylenetriamine triethylenetetramine, propan-1,3-diamine, hexamethylenediamine, aminoethylpiperazine, isophoronediamine, polyamidoamine, diaminodiphenylmethane, diaminodiphenyl ether, diaminodiphenol sulfones, aniline-formaldehyde resins, 2,2,4-trimethylhexane-1,6 diamine, m-xylylenediamine, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, 3-aminomethyl-3,55-trimethylcyclohexylamine
• Methylhexahydrophthal Acidanhydrid and phenols such.
• Phenol aralkyl resin Phenol aralkyl resin, phenoltrimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol kocondensate resin, naphthol cresol kocondensate resin, biphenol-modified phenol resin, and aminotriazine-modified phenol resin.
• the hardeners can be used alone or in combination
• Polymerization are tertiary amines, benzyldimethylamine, N-alkylpyridines, imidazole, 1-Methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-heptadecylimidazole, metal salts of organic acids, Lewis acids and amine complex salts.
• thermoset polymers are preferably those which are derived from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins.
• thermosetting polymers are acrylic resins derived from substituted acrylic acid esters, such as. As of epoxy acrylates, urethane acrylates or polyester acrylates.
• thermoset polymers which are preferably used are alkyd resins, polyester resins and acrylate resins which are blended with melamine resins, urea resins,
• Isocyanates, isocyanurates, polyisocyanates or epoxy resins are crosslinked.
• thermoset polymers are polyurethanes or polyureas obtained by reacting polyisocyanates or ureas with polyols or polyamines.
• Preferred polyols are alkene oxide adducts of ethylene glycol, 1, 2-propanediol, bisphenol A, trimethylolpropane, glycerol, pentaerythrol, sorbitol, sugar or degraded starch. It is also possible to use polyester polyols. These can be obtained by polycondensation of a polyalcohol such as ethylene glycol,
• Dextrose and / or sorbitol with a dibasic acid such as oxalic acid, malonic acid, succinic acid, tartaric acid, adipic acid, sebacic acid,
• Suitable polyisocyanates are aromatic, alicyclic or aliphatic
• Polyisocyanates having not less than two isocyanate groups and mixtures thereof Preference is given to aromatic polyisocyanates, such as tolyl diisocyanate,
• alicyclic polyisocyanates such as methylene diphenyl diisocyanate, tolylene
• Suitable polyisocyanates are also modified products obtained by reaction of polyisocyanate with polyol, urea, carbodiimide and / or biuret.
• thermoplastic polymers particularly preferably polystyrene HI, polyphenylene ethers, polyamides, polyesters, polycarbonates and blends or polymer blends of the type ABS (acrylonitrile-butadiene-styrene) or PC / ABS (polycarbonate / acrylonitrile-butadiene-styrene) or PPE / HIPS
• Polystyrene HI is a polystyrene with increased impact strength.
• thermoplastic polymers used are polyamides, polyesters and PPE / HIPS blends.
• the flame retardant combinations used according to the invention stabilize the polymers (component F) very well against thermal degradation. This is reflected in the change in the specific viscosity of thermoplastic polymers in compounding and shaping of the invention
• the resulting thermal stress has a partial degradation of the polymer chains result, resulting in a reduction of average molecular weight and associated therewith expresses a reduction in the viscosity of a polymer solution.
• the proportion of component F is usually from 25 to 95% by weight, preferably from 25 to 75% by weight.
• the proportion of component F is usually from 25 to 95% by weight, preferably from 25 to 75% by weight.
• Component A usually 1 to 35 wt .-%, preferably 5 to 20 wt .-%.
• the proportion of component B is usually 0.01 to 3 wt .-%, preferably 0.05 to 1, 5 wt .-%.
• the proportion of component C is usually 0.001 to 1% by weight, preferably 0.01 to
• the proportion of component D is usually 1 to 25 wt .-%, preferably 4 to 10 wt .-%.
• the proportion of component E is usually 0 to 10 wt .-%, preferably 1 to 8 wt .-%.
• the percentages for the proportions of components A to F relate to the total amount of the polymer composition.
• Polymer compositions achieve a rating of V0 to UL-94, especially measured on moldings of 3.2 mm to 0.4 mm thickness.
• Polymer compositions have a Glow Wire Flammability Index according to IEC-60695-2-12 greater than or equal to 960 ° C, in particular measured on molded parts of 0.75 - 3 mm thickness.
• the particularly preferred polyamides of component F are generally homo- or copolyamides derived from (cyclo) aliphatic
• Aminocarboxylic acids or their polyamide-forming derivatives, such as their salts derived are examples of aminocarboxylic acids or their polyamide-forming derivatives, such as their salts derived.
• polyamides used according to the invention as component F can be prepared by various processes and synthesized from very different building blocks and, in a specific application, alone or in combination with processing aids, stabilizers or even polymers
• Alloy partners preferably elastomers, to materials equipped with specially selected property combinations.
• elastomers elastomers
• 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 F are preferably partially crystalline aliphatic polyamides having a melting point of less than or equal to 290 ° C., preferably less than or equal to 280 ° C. These can be based on
• cycloaliphatic lactams with at least 5 ring members or corresponding amino acids.
• Suitable starting materials are aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, hexamethylenediamine, 1, 9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane,
• Aminocarboxylic acids preferably aminocaproic acid or the corresponding lactams into consideration.
• Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, most preferably ⁇ -caprolactam is used.
• the aliphatic homo- or copolyamides used according to the invention are preferably polyamide 12, polyamide 4, polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.9, polyamide 6.10, polyamide 6.12, polyamide 6.66, polyamide 7.7, polyamide 8.8, polyamide 9.9, Polyamide 10.9, polyamide 10.10, polyamide 1 1 or polyamide 12.
• polyamide 12 polyamide 4
• polyamide 4.6 polyamide 6
• polyamide 6.6 polyamide 6.9
• polyamide 6.10 polyamide 6.12
• polyamide 6.66 polyamide 7.7, polyamide 8.8, polyamide 9.9
• These are known, for example, under the trade names Nylon® , Fa. DuPont, Ultramid ®, Fa. BASF, Akulon ® K122, Fa. DSM, Zytel ® 7301,
• PA6 PA6.6
• other aliphatic homo- or copolyamide-based compounds in which a
• Polyamide group in the polymer chain 3 to 1 1 come methylene groups.
• Flame retardant polyamide compositions in which one or more polyamides is selected as component G from the group consisting of PA 6, PA 6.6, PA 4.6, PA 12, PA 6.10 are preferably used.
• Flame-retardant polyamide compositions in which polyamide 6.6 or polymer blends of polyamide 6.6 and polyamide 6 are used as component G are particularly preferred.
• component F consists of at least 75% by weight of polyamide 6,6 and at most 25% by weight of polyamide 6.
• the particularly preferred polyesters of component F are generally (cyclo) aliphatic or aromatic-aliphatic polyesters derived from (cyclo) aliphatic and / or aromatic dicarboxylic acids or their polyester-forming derivatives, such as their dialkyl esters or anhydrides, and of (cyclo) aliphatic and / or araliphatic diols or of (cyclo) aliphatic and / or aromatic hydroxycarboxylic acids or their polyester-forming derivatives, such as their alkyl esters or anhydrides.
• (Cyclo) aliphatic includes cycloaliphatic and aliphatic compounds.
• thermoplastic polyesters of component F are preferably selected from the group of polyalkylene esters of aromatic and / or aliphatic dicarboxylic acids or their dialkyl esters.
• Preferably used components F are aromatic-aliphatic thermoplastic polyesters and preferably thermoplastic polyesters derived by reacting aromatic dicarboxylic acids or their polyester-forming derivatives with aliphatic C 2 -C 10 -diols, in particular with C 2 -C 4 -diols.
• preferably used components F are
• Polyalkylene enterephthalates and particularly preferably polyethylene terephthalates or polybutylene terephthalates.
• Polyalkylene terephthalates preferably contain at least 80 mol%, in particular 90 mol%, based on the dicarboxylic acid, units derived from terephthalic acid.
• polyalkylene terephthalates may contain up to 20 mol% of radicals of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or radicals of aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,
• Polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or tribasic or tetrabasic carboxylic acids, as described, for example, in US Pat. As described in DE-A-19 00 270 are branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and pentaerythritol. Particularly preferred components F are polyalkylene terephthalates which are prepared solely from terephthalic acid and its reactive derivatives (eg.,
• Dialkyl esters and ethylene glycol and / or propanediol-1, 3 and / or butanediol-1, 4 (Polyethylene and polytrimethylene and polybutylene terephthalate) and mixtures of these polyalkylene terephthalates.
• Preferred polybutylene terephthalates contain at least 80 mol%
• the preferred polybutylene terephthalates may further contain, in addition to 1,4-butanediol radicals, up to 20 mol% of other aliphatic diols having 2 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, e.g. B. residues of
• Polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components and / or butanediol-1,4.
• the thermoplastic component used as component F according to the invention is also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components and / or butanediol-1,4.
• Polyesters may also be used in admixture with other polyesters and / or other polymers.
• the polymer 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 for antioxidants, antistatic agents, emulsifiers, nucleating agents, plasticizers, Processing aids, impact modifiers, dyes, pigments,
• Fillers reinforcing agents and / or other flame retardants that differ from components A, B, C, D and E.
• These include in particular phosphates, such as melamine
• Preferred metals for this purpose are the elements of FIG. 2.
• Melamine poly are preferably melamine poly (zinc phosphates), melamine poly (magnesium phosphates) and / or melamine poly (calcium phosphates).
• melamine poly metal phosphates
• melamine-intercalated aluminum, zinc or magnesium salts of condensed phosphates very particular preference is given to bis-melamine-zinc-diphosphate and / or bis-melamine-alumotriphosphate.
• Aluminum phosphates Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
• Aluminum phosphates Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
• calcium phosphate Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
• calcium phosphate Preference is given to aluminum phosphates, aluminum monophosphates; Aluminum orthophosphates (AIPO4), aluminum hydrogen phosphate (Al2 (HPO4) 3) and / or aluminum dihydrogen phosphate
• calcium phosphate Preference is given to aluminum phosphates, aluminum
• Polymer composition is usually up to 60 wt .-%, preferably between 10 and 50 wt .-%, based on the total amount of
• Polymer composition Particular preference is given to polymer compositions according to the invention which contain fillers and / or in particular reinforcing materials, preferably glass fibers. It can also be mixtures of two or more
• fillers and / or reinforcing materials are used.
• the proportion of fillers and / or reinforcing materials in the novel Polynnerzusannnener is usually 1 to 45 wt .-%, preferably 20 to 40 wt .-%.
• the further additives G are known per se as additives to Polynnerzusannnneneren and can be used alone or in admixture or in the form of masterbatches.
• the abovementioned components A, B, C, D, F and, if appropriate, E and / or G can be used in a wide variety of combinations to form the invention
• flame-retarded polymer composition are processed. It is thus possible to mix the components into the polymer melt already at the beginning or at the end of the polycondensation or in a subsequent compounding process. Furthermore, there are processing processes in which individual
• Drying process possibly warm up warm polymer granules.
• two or more of the components of the polymer compositions of the present invention may be combined by mixing prior to incorporation into the polymer 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.
• Polymer compositions can also be prepared granules, which can then be introduced into the polymer matrix.
• Polymer 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 polymer composition according to the invention or two or more components thereof may be prepared by roll compaction in one embodiment.
• the polymer 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 polymer composition according to the invention or two or more components thereof can be prepared in one embodiment by spray granulation.
• 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.
• thermosetting polymer compositions When using polymers or precursors thereof, which are processed into thermosetting polymer compositions, different manufacturing processes can be used.
• a process for the preparation of flame-retardant thermosetting compositions is characterized in that a thermosetting resin having a
• Flammschutzmittelkombination invention comprising the above-defined components A, B, C, D and optionally E and optionally with other flame retardants, synergists, stabilizers, additives and fillers or
• thermosetting resin with a flame retardant combination containing the above-defined components A, B, C, D and optionally F and optionally with other flame retardants, synergists, stabilizers, additives and Filling or
• Temperatures for example at temperatures of 80 to 150 ° C, wet presses (hot or hot pressing).
• the invention also relates to moldings produced from the above-described flame-retardant polymer composition comprising the components A, B, C, D and F and optionally the components E and / or G.
• the molded parts according to the invention may be any desired formations. Examples of these are fibers, films or moldings obtainable from the novel flame-retardant polymer molding compositions by any desired molding processes, in particular by injection molding or extrusion.
• the preparation of the flame-retardant polymer moldings according to the invention can be carried out by any molding process. Examples are injection molding, Pressing, foam-molding, gas-injection molding, blow-molding,
• the molded parts are preferably injection-molded parts or extruded parts.
• the flame-retardant polymer 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 polymer 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,
• the invention likewise preferably relates to the use of the flame-retardant polymer compositions according to the invention for the production of moldings in the form of components for the electrical / electronics sector, in particular for parts of printed circuit boards, housings, foils, lines, switches, distributors, relays, resistors, capacitors, coils, lamps , Diodes, LEDs, transistors, connectors, regulators, memories and sensors, in the form of large-area components, in particular of housing parts for control cabinets and in the form of elaborately designed components with sophisticated geometry.
• 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.
• the following examples illustrate the invention without limiting it.
• Polyamide 6.6 (PA 6.6-GV; melting range of 255-260 ° C): Ultramid ® A27 (BASF)
• Polyamide 6 (melting range of 217-222 ° C): Durethan ® B29 (Lanxess)
• Polyamide 6T / 6.6 (melting range 310-320 ° C): Vestamid ® HAT plus 1000 (Evonik)
• PBT Polybutylene terephthalate
• BASF Ultradur ® 4500 (BASF) glass fibers
• the flame retardant components were mixed in the proportions shown in the tables and on the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D) at temperatures of 260 to 310 ° C in PA 6.6 and at 250 to 275 ° C in PA 6 resp at 310 to 330 ° C PA 6T / 6.6 incorporated.
• the glass fibers were over a second side feed 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 250 to 320 ° C to test specimens processed and based on the UL 94 test
• the Glow Wire Flammability Index (GWFI Index) has been determined in accordance with standard IEC-60695-2-12.
• Polymer compositions are measured with an X-ray powder diffractometer (XTert-MPD, Phillips). The sample was irradiated with Cu-K-alpha radiation and the step time was 1 second.
• XTert-MPD X-ray powder diffractometer
• the polyamide compositions of Examples 1 to 5 according to the invention are molding compositions which reach the fire classification UL 94 V-0 at 0.4 mm and at the same time have CTI 500 volts and GWFI 960 ° C.
• the addition of component E in Example 5 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.
• polyamide compositions of Examples 6 to 10 according to the invention are, for example, at the same time having CTI 500 volts and GWFI 960 ° C., which reach the UL 94 V-0 fire rating at 0.4 mm.
• Example 10 leads to a further improvement of the flame retardant
• polyester compositions according to the invention of Examples 1 1 to 15 are molding compositions which reach the fire class UL 94 V-0 at 0.4 mm and at the same time have CTI 500 volts and GWFI 960 ° C.
• component E in Example 15 leads to a further improvement of the flame retardancy expressed by a reduced afterburning time.
• Example V15 In Comparative Example V15, by increasing the concentration of components A, B and C compared to Example V14, although a shortening of the afterburning time. However, this polyester composition still exhibited an extended afterburn time compared to Example 12.
• Test specimens could not be produced from any of the PA molding wettings of Comparative Examples V16-V18, since the PA molding nosings proved to be unprocessable.
• the polyamide strands foamed during production and no test specimens suitable for the measurements could be produced.

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