EP3283564A1 - Verfahren zur herstellung flammwidriger, nicht korrosiver und stabiler polyamidformmassen - Google Patents

Verfahren zur herstellung flammwidriger, nicht korrosiver und stabiler polyamidformmassen

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Publication number
EP3283564A1
EP3283564A1 EP16714400.5A EP16714400A EP3283564A1 EP 3283564 A1 EP3283564 A1 EP 3283564A1 EP 16714400 A EP16714400 A EP 16714400A EP 3283564 A1 EP3283564 A1 EP 3283564A1
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European Patent Office
Prior art keywords
component
weight
aluminum
use according
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP16714400.5A
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German (de)
English (en)
French (fr)
Inventor
Elke Schlosser
Sebastian HÖROLD
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Clariant International Ltd
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Clariant Plastics and Coatings Ltd
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Publication of EP3283564A1 publication Critical patent/EP3283564A1/de
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    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
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    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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    • 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
    • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
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    • C08K7/00—Use of ingredients characterised by shape
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    • C08K7/14—Glass
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • 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 invention relates to a process for the preparation of flame-retardant, non-corrosive and stable polyamide molding compositions and these compositions themselves.
  • Phosphinic acids as effective flame retardant additives proven (DE-A-2252258 and DE-A-2447727). Calcium and aluminum phosphinates have been described as being particularly effective in polyesters, and
  • thermoplastics take place predominantly in the melt.
  • the associated structural and state changes due to temperature and shear hardly survive a plastic without changing its chemical structure.
  • 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.
  • DE-A-102010048025 describes flame retardant-stabilizer combinations for thermoplastic polymers which show good flame retardancy with good mechanical properties and also no discoloration and efflorescence due to polymer degradation and decomposition reactions
  • component A a salt of a dialkylphosphinic acid
  • component B a salt of phosphorous acid
  • component C a zinc-containing additive
  • the invention therefore relates to the use of a mixture of several components as a non-corrosive flame retardant, wherein the
  • R 1 , R 2 are the same or different and C 1 -C 6 -alkyl, linear or branched;
  • R 3 is C 1 -C 10 -alkylene, linear or branched, C 6 -C 10 -arylene, C 7 -C 20 -alkylarylene or C 7 -C 20 -arylalkylene;
  • M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K and / or a protonated nitrogen base;
  • component B from 1 to 80% by weight of a salt of phosphorous acid having the general formula (III)
  • M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na and / or K,
  • component C 0.1 to 30 wt .-% of an inorganic zinc compound
  • component D 0 to 30 wt .-% of a nitrogen-containing synergist and / or a phosphorus / nitrogen flame retardant
  • component E 0 to 3 wt .-% of a phosphonite or a mixture of a phosphonite and a phosphite and
  • component F 0 to 3 wt .-% of an ester or salt of long-chain aliphatic carboxylic acids (fatty acids), which typically have chain lengths of CM to C40, wherein the sum of the components is always 100 wt .-%, contains.
  • R 1 , R 2 in formula (I) and (II) are identical or different and denote methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
  • R 3 is methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene; Phenylene or naphthylene; Methylphenylene, ethyl-phenylene, tert-butylphenylene, methylnaphthylene, ethylnaphthylene or tert-butylnaphthylene; Phenyl-methylene, phenyl-ethylene, phenyl propylene or phenyl-butylene.
  • the mixture contains
  • component A 60 to 89.8% by weight of component A
  • the mixture also contains
  • component F 0.1 to 2% by weight of component F.
  • the mixture contains
  • component A 60 to 84.8% by weight of component A
  • component F 0.1 to 2% by weight of component F.
  • the mixture contains
  • component A 60 to 83.8% by weight of component A
  • component F 0.1 to 2% by weight of component F.
  • Component B is preferably reaction products of phosphorous acid with aluminum compounds. Most preferably, component B is um
  • w 0 to 4.
  • s is 0 to 4, or the aluminum phosphite mixtures of aluminum phosphite of the formula (XII) with sparingly soluble aluminum salts and nitrogen-free foreign ions,
  • Component C) is preferably zinc oxide, zinc hydroxide, tin oxide hydrate, zinc borate, basic zinc silicate and / or zinc stannate.
  • Component D) is preferably condensation products of melamine and / or reaction products of melamine with polyphosphoric acid and / or reaction products of condensation products of the melamine with polyphosphoric acid or mixtures thereof; Meiern, melam, melon, dimelamine pyrophosphate, melamine polyphosphate, melem polyphosphate,
  • the phosphonites (component E)) are those of the general structure
  • R is a mono- or polyhydric aliphatic, aromatic or heteroaromatic organic radical
  • R 2 independently of one another are C 1 -C 12 -alkyl (linear or branched), C 1 -C 12 -alkoxy, C 5 -C 12 -cycloalkyl and
  • m 1 to 4.
  • Component F) is preferably alkali metal, alkaline earth metal,
  • the mixture is introduced from a plurality of components in a polymer.
  • the polymer is polyester, polyamides and / or polymer blends containing polyamides or polyesters.
  • the polymer is particularly preferably one or more polyamides which may be provided with fillers and / or reinforcing materials.
  • the polyamides are preferably in the form of shaped bodies, films, threads and / or fibers.
  • the use according to the invention comprises a composition of
  • Component C) is particularly preferably zinc stannate and / or zinc borate.
  • Component E) is preferably phosphonite or a mixture of a phosphonite and a phosphite.
  • Preferred salts of phosphorous acid are water-insoluble or sparingly soluble salts.
  • Particularly preferred salts of phosphorous acid are aluminum, calcium and zinc salts.
  • component B) is a
  • Reaction product of phosphorous acid and an aluminum compound Reaction product of phosphorous acid and an aluminum compound.
  • Aluminiumphosphite of the type preferred are Al2 (HPO3) 3 * 0.1 to 30 Al2O3 * 0 - 50 H 2 O, particularly preferably Al2 (HPOs) 3 * 0.2 to 20 Al2O3 * 0 - 50 H2O, most preferably Al2 ( HPOs) 3 * 1 - 3 AI2O3 * 0 - 50 H2O.
  • Mixtures of aluminum hydroxide and aluminum phosphite of composition 5, are preferred - 95 wt .-% Al2 (HPO3) 3 * nH2O and 95 - 5 wt .-% Al (OH) 3, more preferably 10 - 90 wt .-% Al2 (HPO3) 3 * nH2O and 90 - 10 wt .-% Al (OH) 3 , most preferably 35 - 65 wt .-% Al 2 (HPO3) 3 * nH 2 O and
  • the aluminum phosphites have particle sizes of 0.2 to 100 ⁇ .
  • the preparation of the preferred aluminum phosphites is usually accomplished by reacting an aluminum source with a source of phosphorus and optionally a template in a solvent at 20 to 200 ° C for a period of up to 4 days.
  • Aluminum source and phosphorus source are mixed, heated under hydrothermal conditions or at reflux, filtered off, washed and dried.
  • Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
  • Preferred sources of phosphorus are phosphorous acid, (acidic)
  • Preferred Alkaliphosphite are disodium phosphite, Dinatriumphosphithydrat, 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.
  • Component C) is preferably zinc stannate.
  • Suitable components D) are also compounds of the formulas (XV) to (XX) or mixtures thereof
  • R 5 to R 7 are hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or -alkylcycloalkyl, possibly substituted by a hydroxy or a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 -C -alkoxy, Acyl, acyloxy, Ce-Ci2-aryl or -Arylalkyl, -OR 8 and -N (R 8 ) R 9 , as well as N-alicyclisch or N-aromatic,
  • R 8 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or -alkylcycloalkyl, possibly substituted by a hydroxy or a C 1 -C 4 -hydroxyalkyl function, C 2 -C 8 -alkenyl, C 1 -C -alkoxy, -acyl, Acyloxy or C 6 -C 12 aryl or arylalkyl,
  • R 9 to R 13 have the same groups as R 8 and -OR 8 ,
  • n and n independently of one another 1, 2, 3 or 4,
  • Particularly suitable components D) are benzoguanamine,
  • M in formula (I) and (II) is calcium, aluminum or zinc.
  • Protonated nitrogen bases are preferably understood to mean the protonated bases of ammonia, melamine, triethanolamine, in particular NH 4 + .
  • Suitable phosphinates are described in PCT / WO97 / 39053, which is incorporated herein by reference.
  • Particularly preferred phosphinates are aluminum, calcium and
  • the same salt of phosphinic acid as the phosphorous acid is used in the application, so z.
  • UV absorbers and light stabilizers Antioxidants, UV absorbers and light stabilizers, metal deactivators, peroxide-destroying compounds, polyamide stabilizers, basic
  • Co-stabilizers nucleating agents, fillers and reinforcing agents, other flame retardants and other additives.
  • Suitable antioxidants include alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol; 1 .2 Alkylthiomethylphenole, z. B. 2,4-dioctylthiomethyl-6-tert-butylphenol; Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol; Tocopherols, e.g. B. ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E); Hydroxylated thiodiphenyl ethers, e.g. B.
  • O, N and S benzyl compounds e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydi benzyl ether; Hydroxybenzylated malonates, e.g. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydrorybenzyl) -malonate; Hydroxybenzyl aromatics, e.g. B.
  • Suitable UV absorbers and light stabilizers are, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole;
  • 2-hydroxybenzophenones such as.
  • Esters of optionally substituted benzoic acids such as.
  • nickel compounds such as. B. nickel complexes of 2,2'-thio-bis [4 (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of
  • 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as methyl or ethyl esters, nickel complexes of ketoximes, such as 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4 lauroyl-5-hydroxy-pyrazole, optionally with additional ligands; Sterically hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidyl) sebacate; Oxideklarediamide, such as. B. 4,4'-di-octyloxy-oxanilide; 2- (2-hydroxyphenyl) -1, 3,5-triazines, such as. B. 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine.
  • ketoximes such as 2-hydroxy-4-methylphenyl undecylketoxime
  • Suitable metal deactivators are, for. B. ⁇ , ⁇ '-Diphenyloxalklarediamid, N-salicylal-N'-salicyloylhydrazin, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4 -hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) -oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis-phenylhydrazide, ⁇ , ⁇ '-diacetyl-adipic acid dihydrazide, N , N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic di
  • Suitable peroxide-destroying compounds are, for. B. esters of .beta.-thionipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulphide, pentaerythritol tetrakis (.beta.-dodecylmercapto), propionate.
  • esters of .beta.-thionipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester
  • mercaptobenzimidazole the zinc salt of 2-mercaptobenzimidazole
  • zinc dibutyl dithiocarbamate dioctadecyl disulphide
  • pentaerythritol tetrakis
  • Suitable polyamide stabilizers are, for. As copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
  • Suitable basic co-stabilizers are melamine, polyvinylpyrrolidone,
  • Suitable nucleating agents are for.
  • the fillers and reinforcing agents include, for. As calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite and others. As further flame retardants z. As aryl phosphates, phosphonates, salts of hypophosphorous acid and red phosphorus suitable.
  • plasticizers As plasticizers, expandable graphite, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • Additional additives can be added to the polymers before, together with or after addition of the flame retardants.
  • the dosing of both these additives as well as the flame retardants can be carried out as a solid, in solution or melt, as well as in the form of solid or liquid mixtures or as masterbatches / concentrates.
  • the radicals are preferred for the phosphonites
  • R is C4-C18-alkyl (linear or branched), C4-C18-alkylene (linear or branched), C5-C12-cycloalkyl, C5-C12-cycloalkylene, C6-C24-aryl or -heteroaryl, C6-C24-arylene or heteroaryls, which may also be further substituted;
  • R1 is a compound of structure (V) or (VI) with
  • R 2 independently of one another are C 1 -C 8 -alkyl (linear or branched), C 1 -C 8 -alkoxy, -cyclohexyl;
  • Ci-Cs-alkylene linear or branched
  • R is cyclohexyl, phenyl, phenylene, biphenyl and biphenylene
  • R1 is a compound of structure (V) or (VI) with
  • R 2 independently of one another are C 1 -C 8 -alkyl (linear or branched), C 1 -C 8 -alkoxy,
  • Suitable as component F are esters or salts of long-chain aliphatic carboxylic acids (fatty acids), which typically have chain lengths of CM to C40.
  • the esters are reaction products of said carboxylic acids with conventional polyhydric alcohols, such as.
  • ethylene glycol glycerol, trimethylolpropane or pentaerythritol.
  • salts of above-mentioned carboxylic acids are, in particular, alkali metal or alkaline earth metal salts or aluminum and zinc salts.
  • the component F) is esters or salts of stearic acid such as. As glycerol monostearate or calcium stearate.
  • Component F) is preferably reaction products of montan wax acids with ethylene glycol.
  • the reaction products are preferably a mixture of ethylene glycol mono-montan wax acid ester, ethylene glycol dimontane wax acid ester, montan wax acids and ethylene glycol.
  • Component F) is preferably reaction products of montan wax acids with a calcium salt.
  • reaction products are particularly preferably a mixture of 1,3-budanediol mono-montan wax acid ester, 1,3-budanediol di-montan wax acid ester, montan wax acids, 1,3-butanediol, calcium montanate and the calcium salt.
  • Field of application contains the flame retardant combination 20 to
  • Component D) becomes 0 to
  • the flame retardant-stabilizer combination in the polyamide molding composition in a total amount of 2 to 50 wt .-%, based on the Plastic molding compound, used.
  • the amount of polymer is then 50 to 98 wt .-%.
  • the flame retardant combination in the plastic molding composition in a total amount of 10 to 30 wt .-%, based on the plastic molding composition used.
  • the amount of polymer is then 70 to 90 wt .-%.
  • the polymer moldings, films, filaments and fibers contain the flame retardant stabilizer combination in a total amount of 2 to 50 wt .-%, based on the polymer content.
  • the amount of polymer is then 50 to 98 wt .-%.
  • the polymer moldings, films, threads and fibers particularly preferably contain the flame retardant combination in a total amount of from 10 to 30% by weight, based on the polymer content.
  • the amount of polymer is then 70 to 90 wt .-%.
  • additives can be introduced into the plastic in a wide variety of process steps.
  • polyamides already at the beginning or at the end of the polymerization / polycondensation or in a subsequent compounding process, the additives in the polymer melt
  • the polymers are preferably 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, Nylon® 4, Fa. DuPont), polyamide 4/6
  • Ultramid ® A3, BASF polyamide 6/9 (poly (hexamethylene nonanediamid), nylon 6/9 ®, DuPont), polyamide 6/10 (poly (hexamethylene sebacamide), nylon ® 6/10. DuPont), polyamide 6/12 (poly (hexamethylene dodecanediamide), nylon ® 6/12, from DuPont), polyamide 6/66 (poly (hexamethylene adipamide-co-caprolactam), nylon ® 6/66, Fa DuPont), polyamide 7 (poly-7-aminoheptanoic acid, nylon ® 7, from DuPont), polyamide 7,7
  • an elastomer as modifier e.g. As poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide.
  • Polypropylene glycol or polytetramethylene glycol Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
  • the polymers are preferably polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and
  • the polymers are preferably polyesters which differ from
  • Derive dicarboxylic acids and dialcohols and / or hydroxycarboxylic acids or the corresponding lactones such as polyethylene terephthalate,
  • Polybutylene terephthalate (Celanex ® 2500, Celanex ® 2002, from Celanese;. Ultradur ®, BASF), poly-1, 4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and also block polyether esters derived from hydroxyl-terminated polyethers; also with polycarbonates or MBS modified polyester.
  • the invention also relates to a process for the preparation of flame-retardant polymer moldings, characterized in that flame-retardant polymer molding compositions of the invention are produced by injection molding (for example, Aarburg Allrounder injection molding machine) and presses,
  • Foam injection molding, internal gas pressure injection molding, blow molding, film casting, calendering, laminating or coating at higher temperatures to the flame-retardant polymer molded body is processed.
  • the polyamides are preferably those of the amino acid type and / or of the diamine-dicarboxylic acid type.
  • Preferred polyamides are polyamide 6 and / or polyamide 66 and
  • the polyamides are preferably unchanged, dyed, filled, unfilled, reinforced, unreinforced or otherwise modified. Examples
  • Polyamide 6.6 (PA 6.6 GV): Ultramid ® A27 (BASF AG, Germany.)
  • DEPAL diethylphosphinic acid
  • PHOPAL Aluminum salt of phosphorous acid
  • Anti-corrosion additive (component C)):
  • Boehmites Disperal ® 20, Siral 10 ®, ® Pural SB, Sasol, D.
  • Melamine polyphosphate (MPP as hereinafter) Melapur ® 200 (BASF, D.) Phosphonites (component E)): Sandostab ® P-EPQ, Clariant GmbH, D wax components (component F)).:
  • the flame retardant components were mixed in the ratio indicated in the table with the phosphonite, the lubricants and stabilizers, and via the side feeder of a twin-screw extruder (Leistritz ZSE 27 / 44D type) at temperatures of 260 to 310 ° C in PA 6.6 or at 300 - 340 ° C in PPA.
  • the glass fibers were added via a second side feed.
  • the homogenized polymer strand was stripped off, cooled in a water bath and then granulated.
  • Injection molding machine (type Arburg 320 C Allrounder) processed to test specimens at melt temperatures of 250 to 340 ° C and based on the UL 94 test
  • V-0 no afterburning for more than 10 seconds, sum of afterburning times for 10 flame treatments not greater than 50 seconds, no burning dripping, no complete burning off of the sample, no afterglowing of the samples longer than 30 seconds after end of flame
  • V-1 no afterburning for more than 30 seconds after end of flame, sum of afterburning times for 10 flame treatments not greater than 250 seconds, no afterglowing of samples longer than 60 seconds after flaming end, other criteria as for V-0
  • V-2 Ignition of the cotton by burning dripping, other criteria as in V-1
  • MVR Melt volume index
  • a wear parameter is the weight loss of the specimens, which is determined by differential weighing of the specimens with an A & D "Electronic Balance"
  • Mass determination of the specimens was carried out before and after the corrosion test with 25 kg each of steel 1 .2379 or 10 kg polymer throughput on steel CK 45.
  • test slides are removed and physically / chemically cleaned of the adhering plastic.
  • the physical cleaning is done by removing the hot plastic mass by rubbing with a soft material (cotton).
  • the chemical cleaning is carried out by heating the specimens at 60 ° C in m-cresol for 20 minutes. After boiling, still adhering plastic compound is removed by rubbing with a soft cotton swab.
  • Table 1 PA 66 GF 30 Comparative examples with DEPAL and DEPAL / PHOPAL mixtures.
  • Table 2 shows comparative examples V6 to V12 in which a
  • MPP Melamine polyphosphate
  • Stabilizers and / or zinc stannate can be significantly reduced corrosion. Boehmites also lead to a reduction in corrosion. Nevertheless, the loss of mass on the steel plates, caused by corrosion, remains measurable.
  • Table 3 shows as comparative examples glass fiber reinforced PA 66 compounds containing a DEPAL / PHOPAL mixture and non-zinc containing additives. These additives reduce corrosion, but still show measurable loss of mass on the steel platelets. PA 66 GF30 Comparative Examples V13-V17 with DEPAL / PHOPAL mixture and non-zinc anticorrosive additives.
  • Table 4 shows the polyanidine surfactants B1 to B5 according to the invention.
  • Table 5 shows in direct comparison a DEPAL-PHOPAL-containing PPA molding compound V13 and a PPA molding composition according to the invention which contains DEPAL-PHOPAL zinc stannate.
  • the corrosion caused by DEPAL-PHOPAL could be reduced so much by the addition of zinc stannate that in the corrosion test no mass loss at the platelets was more measurable.
  • the molding composition of the invention shows high fire protection requirements according to UL 94 and good mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Fireproofing Substances (AREA)
EP16714400.5A 2015-04-13 2016-04-04 Verfahren zur herstellung flammwidriger, nicht korrosiver und stabiler polyamidformmassen Withdrawn EP3283564A1 (de)

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PCT/EP2016/057313 WO2016165966A1 (de) 2015-04-13 2016-04-04 Verfahren zur herstellung flammwidriger, nicht korrosiver und stabiler polyamidformmassen

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CN108102361A (zh) * 2017-11-22 2018-06-01 浙江大学 有机亚磷酸铝协同的无卤阻燃复配体系及其在玻纤增强工程塑料中的应用
CN107698798A (zh) * 2017-11-22 2018-02-16 江苏利思德新材料有限公司 玻纤增强尼龙用不含氮无卤阻燃复配体系及其应用
CN107760023A (zh) * 2017-11-22 2018-03-06 江苏利思德新材料有限公司 一种玻纤增强尼龙用无卤阻燃复配体系及其应用
CN107778527A (zh) * 2017-11-22 2018-03-09 江苏利思德新材料有限公司 一种基于磷铝化合物的无卤阻燃复配体系及其在玻纤增强工程塑料中的应用
CN107936297A (zh) * 2017-11-22 2018-04-20 江苏利思德新材料有限公司 玻纤增强尼龙用无卤阻燃复配体系及其在无卤阻燃玻纤增强尼龙材料中的应用
CN107936055A (zh) * 2017-11-22 2018-04-20 浙江大学 一种有机亚磷酸铝及其制备方法和应用
CN108948430B (zh) * 2018-06-28 2020-07-07 浙江大学 二烷基单硫代次磷酸盐、有机亚磷酸盐及含氮化合物协同的无卤阻燃体系及其应用
CN108794807B (zh) * 2018-06-28 2020-06-19 浙江大学 二烷基单硫代次磷酸盐、无机亚磷酸盐及含氮化合物协同的无卤阻燃体系及其应用
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CN108997612A (zh) * 2018-08-09 2018-12-14 江苏利思德新材料有限公司 利用无机亚磷酸金属盐提高热稳定性的磷氮无卤阻燃剂组合物及其应用
WO2020147943A1 (en) 2019-01-16 2020-07-23 Clariant Plastics & Coatings Ltd Flame retardant mixture
DE102019201727A1 (de) * 2019-02-11 2020-08-13 Clariant Plastics & Coatings Ltd Flammschutzmittelmischung für thermoplastische Polymere
US20220049120A1 (en) * 2019-04-29 2022-02-17 Hewlett-Packard Development Company, L.P. Three-dimensional printing
WO2021043929A1 (en) * 2019-09-06 2021-03-11 Dsm Ip Assets B.V. Flame retardant polyamide-based 3d printing extrusion materials
CN114450290A (zh) * 2019-09-11 2022-05-06 科莱恩国际有限公司 金属络合物、其制造方法、包含它的阻燃剂聚合物组合物及它们的用途
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DE102015004662A1 (de) 2016-10-13
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JP2018516288A (ja) 2018-06-21
US20180119017A1 (en) 2018-05-03
CN107223149A (zh) 2017-09-29
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