Classifications

• • 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
  • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/14—Glass
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
  • C08K5/098—Metal salts of carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • 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
  • C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a flame retardant
• plastics Due to their chemical composition, many plastics are easily combustible. In order to be able to achieve the high flame retardance requirements demanded by plastics processors and partly by the legislator, plastics generally have to be equipped with flame retardants. These are a variety of different flame retardants and
• Flammschutzmittelsynergisten 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.
• the salts of phosphinic acids have proven to be particularly effective for thermoplastic polymers (DE-A-2 252 258 and DE-A-2 447 727.
• thermoplastic polymers DE-A-2 252 258 and DE-A-2 447 727.
• some derivatives of this flame retardant class in particular due to their low estimated negative influence on the mechanical properties of the thermoplastic molding compositions.
• thermoplastics take place predominantly in the melt.
• the associated structural and state changes hardly survive a plastic without changing its chemical structure.
• antioxidants and stabilizers are used so that the plastic without chemical damage survives the processing 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
• Plastic melt on hot machine parts act as a dispersant for pigments, fillers and reinforcing materials.
• flame retardants the stability of
• Plastics are processed during processing in the melt.
• Flame retardants must often be added in high doses to ensure sufficient flame retardancy of the plastic according to international standards sure. Due to their chemical reactivity, which is required for the flame retardancy at high temperatures, can
• Flame retardants affect the processing stability of plastics. For example, increased polymer degradation, crosslinking reactions, outgassing or discoloration may occur.
• Polyamides are z. B. stabilized by small amounts of copper halides and aromatic amines and hindered phenols, with the achievement of long-term stability at high continuous service temperatures in the foreground (H. Zweifel (Ed.): "Plastics Additives Handbook", 5 th Edition, Carl Hanser Verlag , Kunststoff, 2000, pages 80 to 84).
• Polyamides proved the effect of the stabilizers described so far as insufficient, especially to suppress the effects occurring during processing, such as discoloration and molecular weight reduction.
• thermoplastic polyamide compositions based on phosphinate-containing flame retardant systems to provide that have high thermal stability and no migration effects show good flowability and high electrical values (CTI> 550V) and good flame retardance (UL94 VO to 0.4 mm). It has now surprisingly been found that the thermal stability in
• phosphinate-containing flame-retardant thermoplastic polyamides significantly improved and the tendency to migrate can be reduced if the
• Molding composition in addition to the phosphinates (component B) contains a salt of phosphorous acid (also referred to as phosphonic acid) as component C.
• phosphorous acid also referred to as phosphonic acid
• the polyamide composition contains as component D fillers and / or reinforcing materials.
• the polyamide composition according to the invention as component E
• Carboxyl (ester) amides included.
• inventive polyamide composition as
• Component F is a phosphonite or a phosphonite / phosphite mixture and as component G is an ester or a salt of long-chain aliphatic
• Carboxylic acids (fatty acids), which typically have chain lengths of C14 to C 40 contain.
• the invention is therefore a flame retardant
• thermoplastic resin as component A 1 to 96 wt .-% of one or more thermoplastic
• Polyamides, as component B from 2 to 25% by weight of a dialkylphosphinic acid salt of the formula (I) and / or of a diphosphinic acid salt of the formula (II) and / or their polymers,
• R 1 , R 2 are the same or different and are C 1 -C 6 -alkyl, linear or branched or H:
• Ci-C 10 alkylene is branched, linear or, C 6 -C 0 -arylene, C 7 -C 2 o alkylarylene or C 7 -C 2 o 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; m 1 to 4;
• component D 1 50% by weight of filler or reinforcing material
• component E 0 to 2% by weight of a carboxylesteramide
• component F 0 to 1 wt .-% of a phosphonite or a mixture of a phosphonite and a phosphite and
• the flame retardant polyamide composition contains
• component G 0.1 to 1% by weight of component G.
• the flame-retardant polyamide composition contains 16 to 91, 8 wt .-% of component A,
• component G 0.1 to 1% by weight of component G.
• the flame retardant polyamide composition contains From 16 to 82.7% by weight of component A,
• component G 0.1 to 1% by weight of component G.
• Another preferred flame retardant polyamide composition contains from 26 to 72.7% by weight of component A,
• component G 0.1 to 1% by weight of component G.
• the flame retardant polyamide composition is characterized by having a comparative tracking index measured according to International Electrotechnical Commission Standard IEC-60112/3 of greater than 550 volts.
• the flame retardant polyamide composition is also thereby.
• the flame retardant polyamide composition has a Glow Wire Flammability Index according to IEC-60695-2-12 of 960 ° C at 0.75 - 3 mm thickness.
• the polyamide (PA) is preferably selected from the group PA 6, PA 6,6, PA 4,6, PA 12, PA 6,10, PA 6T / 66, PA 6T / 6, PA 4T, PA 9T, PA 10T , Polyamide copolymers, polyamide blends and combinations thereof.
• Component A is preferably polyamide 66 or copolymers or polymer blends of polyamide 66 and polyamide 6.
• Component A preferably comprises at least 75% by weight of polyamide 66 and at most 25% by weight of polyamide 6.
• polyamide 66 It is also preferably a blend of polyamide 66 and an amorphous, partly aromatic polyamide.
• R 2 are preferably identical or different and denote methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl and / or phenyl.
• Methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or n-dodecylene is preferably the component BR 3 ; Phenylene or naphthylene; Methyl-phenylene, ethyl-phenylene, tert-butylphenylene, methyl-naphthylene, ethyl-naphthylene or tert-butylnaphthylene; Phenyl-methylene, phenyl-ethylene, phenyl-propylene or phenyl-butylene.
• the salt of the phosphorous acid (component C) of the general formula (III) preferably corresponds to
• the salt of the phosphorous acid (component C) is preferably aluminum phosphite [Al (H 2 PO 3 ) 3 ], secondary aluminum phosphite [Al 2 (HPO 3 ) 3 ], basic aluminum phosphite [Al (OH) (H 2 PO 3 ) 2 * 2aq]
• Aluminum phosphite tetrahydrate [Al 2 (HPO 3) 3 * 4aq], aluminum phosphonate, Al 7 (HPO 3 ) 9 (OH) 6 (1,6-hexanediamine) 1 , 5 * 12H 2 O, ⁇ 2 ( ⁇ O 3 ) 3 * ⁇ 2 ⁇ 3 * ⁇ 2 ⁇ with x 2.27-1 and / or Al H 6 Pi 6 0 18 .
• the salt of the phosphorous acid (component C) is preferably also aluminum phosphites of the formulas (I), (II) and / or (III), wherein
• Formula (II) AI 2 , ooM z (HP0 3 ) y (OH) vx (H 2 O) w comprises and
• M is alkali metal ions, z is 0.01 to 1.5, and y is 2.63 to 3.5 and v is 0 to 2 and w is 0 to 4;
• Aluminum phosphite tetrahydrate [Al 2 (HPO 3 ) 3 * 4aq] to give aluminum phosphonate, Al ⁇ HPOaMOHM .e-hexanediamine ⁇ ⁇ h O, Al 2 (HPO 3 ) 3 * xAl 2 0 3 * nH 2 0 where x 2 , 27 - 1 and / or AI 4 H 6 P 16 0 18 .
• the component C has an average particle size of from 0.2 to
• the reinforcing filler is glass fibers.
• the component E is a derivative of a
• Component E is more preferably N, N'-bis-piperdinyl-1,3-benzenedicarboxamide and / or N, N'-bis (2,2,6,6-tetramethyl-4-piperdinyl) -1, 3-benzenedicarboxamide.
• the phosphonites (component F) are those of the general structure
• R is a mono- or polyhydric aliphatic, aromatic or heteroaromatic organic radical
• a direct bond O, S, C 1 -C -alkylene (linear or branched) or C 1 -C -alkylidene (linear or branched),
• R 2 independently of one another CIC 12 alkyl (linear or branched), CrCl 2 -alkoxy and / or C 5 -C 2 represent cycloalkyl and n is 0 to 5 and m is 1 to 4.
• Component G is preferably alkali metal, alkaline earth metal,
• the invention also relates to a three-dimensional article comprising the flame-retardant polyamide composition according to one or more of claims 1 to 23, characterized in that these are shaped articles, injection-molded parts, extruded materials and parts.
• flame retardant polyamide compositions have a good flame retardancy combined with improved thermal and hydrolytic stability.
• the addition of a carboxylesteramide improves the processing.
• the polymer degradation is prevented or greatly reduced and there are no moldings and no efflorescence observed.
• flame-retardant polyamide compositions according to the invention show only slight discoloration in the course of processing in the melt.
• compositions according to the invention contain at least one thermoplastic polyamide.
• thermoplastic polyamides are based on Hans
• inventively preferred polyamides can according to various aspects
• Processes are prepared and synthesized from very different building blocks and in a particular application alone or in combination with
• Property combinations are equipped. Also suitable are blends with Levels of other polymers, preferably of polyethylene, polypropylene, ABS, wherein optionally one or more compatibilizers can be used.
• the properties of the polyamides can be improved by adding elastomers, for. In terms of impact strength, especially if they are reinforced polyamides. The multitude of possible combinations enables a very large number of products with different properties.
• Monomerbausteine various chain regulators for setting a desired molecular weight or monomers with reactive groups for later intended post-treatments can be used.
• Preferred polyamides to be used as component A are partially crystalline
• Polyamides which can be prepared starting from diamines and dicarboxylic acids and / or lactams with at least 5 ring members or corresponding amino acids.
• Suitable starting materials are aliphatic and / or aromatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid, sebacic acid, isophthalic acid, terephthalic acid, aliphatic and / or
• aromatic diamines preferably tetramethylenediamine, hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, the isomeric diaminodicyclohexylmethanes, diaminodicyclohexylpropanes, bisaminomethylcyclohexane, phenylenediamines, xylylenediamines, aminocarboxylic acids, preferably aminocaproic acid or the corresponding Lactams are considered.
• Copolyamides of several of the monomers mentioned are included. Particularly preferred are caprolactams, very particularly preferred
• [epsilon] -caprolactam used. Most particularly suitable are most PA6, PA66 and other aliphatic and / or aromatic polyamides or copolyamides
• the polyamides and copolyamides 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 11, polyamide 12, etc. These are z. B under the tradename Nylon ®, DuPont, Ultramid ®, BASF, Akulon ® K122, from DSM, Zytel ® 7301, from DuPont....; Durethan ® B 29, Messrs. Bayer and
• aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally an elastomer as a modifier, for.
• poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers, or with polyethers, such as. B. with
• Polyethylene glycol polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM polyamide systems").
• compositions in addition to the invention used
• thermoplastic polyamide at least one further thermoplastic polymer, more preferably at least one other polyamide.
• blends of polyamide 66 and one or more partially aromatic, amorphous polyamides are also preferred.
• thermoplastic polyamide in addition to the thermoplastic polyamide in a preferred embodiment
• Embodiment additionally to be used polymers conventional additives, in particular mold release agents, stabilizers and / or flow aids can be added in the melt or applied to the surface.
• thermoplastic polyamides of component A may be synthetically synthesized e.g. be derived from petrochemical raw materials and / or chemical or biochemical processes from renewable raw materials
• flame retardants or flame retardant synergists can be used.
• nitrogen-containing flame retardants such as melamine cyanurate, condensed elamine (Meiern, Melon) or melamine phosphates and melamine polyphosphates can be added.
• Other phosphorus flame retardants such as aryl phosphates, red phosphorus or phosphazenes may also be used.
• Flame retardant additives such as aluminum and / or magnesium hydroxide, Ca-Mg-carbonate hydrates (e.g., DE-A 4,236,122). Flammschutzstoffsynergisten from the group of oxygen-nitrogen or sulfur-containing metal compound, preferably zinc oxide, zinc borate,
• Calcium borate magnesium borate or mixtures thereof.
• suitable flame retardant additives are carbon formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, Polyethersulfone or polyether ketones and anti-dripping agents, in particular tetrafluoroethylene polymers.
• the flame retardants can be added in pure form, as well as masterbatches or compactates.
• Component B is preferably the aluminum or zinc salt of diethylphosphinic acid.
• q is 0.01 to 0.1.
• z is preferably 0.15 to 0.4;
• u is preferably from 2.834 to 2.99; t is 0.332 to 0.03 and s is 0.01 to 0.1.
• the flame-retardant according to the invention As component D, the flame-retardant according to the invention
• Polyamide compositions in a further preferred embodiment contain at least one filler or reinforcing material.
• Mixtures of two or more different fillers and / or reinforcing materials preferably based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicic acids, nanoscale minerals, particularly preferably montmorillonites or nano-boehmite, may also be used.
• Carbon fibers and / or glass fibers are used. Preference is given to mineral particulate fillers based on talc, mica, silicate, quartz, titanium dioxide, wollastonite, kaolin, amorphous silicas,
• needle-shaped mineral fillers are also particularly preferably used. Under needle-shaped mineral fillers is understood according to the invention a mineral filler with pronounced needle-like character.
• acicular wollastonites are mentioned.
• the mineral preferably has a length to diameter ratio of 2: 1 to 35: 1, more preferably from 3: 1 to 19: 1, particularly preferably from 4: 1 to 12: 1.
• the mean particle size of the acicular minerals according to the invention is preferably less than 20 ⁇ m, particularly preferably less than 15 ⁇ m,
• the filler and / or reinforcing material may in a preferred
• Be surface-modified embodiment preferably with a
• Adhesive or adhesion promoter system particularly preferably based on silane.
• pretreatment is not essential. Especially at
• glass fibers can be added to silanes as well
• Fiber processing aids are used.
• the invention very particularly preferably as component D.
• glass fibers which generally have a fiber diameter between 7 and 18 ⁇ , preferably between 9 and 15 [im have, as
• Continuous fibers or added as cut or ground glass fibers may be provided with a suitable sizing system and a primer or primer system, preferably based on silane.
• the compositions of the invention may contain other additives. Preferred additives for the purposes of the present invention are
• UV stabilizers UV stabilizers, gamma ray stabilizers,
• Hydrolysis stabilizers Hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, Plasticizers, processing aids, impact modifiers, dyes and pigments.
• the additives may be used alone or in admixture or in the form of
• Suitable antioxidants include alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol; Alkylthiomethylphenols, eg. 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.
• 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol; O-, N- and S-benzyl compounds, eg 3,5,3 ', 5'-tetra-tertiary butyl-4,4'-dihydroxydi-benzyl ethers; hydroxybenzylated malonates, e.g., dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydrorybenzyl) malonate; hydroxybenzyl aromatics, e.g.
• 4-Hydroxauric acid amide 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester; Esters of ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols; Esters of .beta .- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with or without
• esters of ⁇ - (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols
• Particularly preferred are sterically hindered phenols alone or in
• N, N'-bis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionyl] hexamethylenediamine eg Irganox 5 098 Fa. BASF SE, Ludwigshafen, Germany
• 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. For example, 4-hydroxy, 4-methoxy, 4-octoxy,
• Esters of optionally substituted benzoic acids such as.
• colorants are preferably inorganic pigments, in particular
• Titanium dioxide, ultramarine blue, iron oxide, zinc sulfide or carbon black, and further organic pigments, preferably phthalocyanines, quinacridones, perylenes and dyes, preferably nigrosine and anthraquinones are used.
• 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,
• Dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth salts of higher fatty acids for example, Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony catechinate or tin catechinate.
• Suitable nucleating agents are, for. As 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid, alumina or silica and most preferably talc, this list is not exhaustive.
• the MFI Melt Flow Index
• ISO 1133 or ASTM D 1238 The MFI or all information on the MFI in the context of the present invention relate or have become uniform according to ISO 1133 measured and determined at 190 ° C and a test weight of 2.16 kg.
• plasticizers are dioctyl phthalate,
• Dibenzyl phthalate butyl benzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.
• the present invention also relates to products, preferably fibers, films or moldings, obtainable from the compositions according to the invention by injection molding or extrusion.
• Suitable phosphinates (component B) are described in PCT / WO97 / 39053, to which reference is expressly made.
• Particularly preferred phosphinates are aluminum, calcium and zinc phosphinates.
• Preferred salts of phosphorous acid are water-insoluble or sparingly soluble salts.
• Particularly preferred salts of phosphorous acid are the aluminum, the calcium and the zinc salts
• component C is a
• Reaction product of phosphorous acid and an aluminum compound Preference is given to aluminum phosphors having the CAS numbers 15099-32-8, 119103-85-4, 220689-59-8, 56287-23-1, 156024-71-4, 71449-76-8 and
• the aluminum phosphors preferably have particle sizes of 0.2-100 ⁇ m
• the preparation of the preferred aluminum film is accomplished by reacting an aluminum source with a source of phosphorus 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. dried at 110 ° C.
• Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride, aluminum hydroxide (eg pseudoboehmite).
• Preferred sources of phosphorus are phosphorous acid, (acidic)
• alkali metal phosphites are disodium phosphite, disodium phosphite hydrate, trisodium phosphite, potassium hydrogen phosphite
• Preferred disodium phosphite hydrate is ⁇ Brüggolen H10 from 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 dialkylphosphinate together with aluminum phosphite or Zinkdialkylphosphinat together with zinc phosphite.
• Component G is preferably alkali metal, alkaline earth metal,
• Aryl phosphates, phosphonates, salts of hypophosphorous acid and red phosphorus are preferably suitable as further flame retardants.
• the radicals are preferred for the phosphonites
• R 1 is a compound of structure (V) or (VI) with
• R 2 is independently C 1 -C 8 -alkyl (linear or branched), C is Cs-alkoxy, cyclohexyl;
• R 1 is a compound of structure (V) or (VI) with
• R 2 independently of one another CiC 8 alkyl (linear or branched), Ci-C 8 alkoxy, cyclohexyl
• Heteroaromatics such as benzene, biphenyl or diphenyl ether with
• Phosphorus trihalides preferably phosphorus trichloride
• a Friedel-Crafts catalyst such as aluminum chloride, zinc chloride, iron chloride, etc.
• phosphites those arise after the said reaction sequence from excess phosphorus trihalide and the phenols described above.
• n can be 0 or 1 and these mixtures optionally continue
• Parts of the compound (X) or (XI) may contain:
• Suitable as component G are esters or salts of long-chain aliphatic carboxylic acids (fatty acids), which typically have chain lengths from C14 to C 40th
• the esters are reaction products of said carboxylic acids with conventional polyhydric alcohols, such as.
• polyhydric alcohols such as.
• Suitable salts of the carboxylic acids mentioned are, in particular, alkali metal or alkaline earth metal salts or aluminum and zinc salts.
• the component G is esters or salts of stearic acid such as. As glycerol monostearate or calcium stearate.
• Component G 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 di-montan wax acid ester, montan wax acids and ethylene glycol.
• Component G is preferably reaction products of montan wax acids with a calcium salt.
• the reaction products are particularly preferably a mixture of 1,3-budanediol mono-montan wax acid ester, 3-budanediol di-montan wax acid ester, montan wax acid, 1,3-butanediol, calcium montanate and the calcium salt.
• the abovementioned additives can be introduced into the plastic in a wide variety of process steps. Thus, it is possible with 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 invention also relates to a process for the preparation of flame-retardant polymer moldings, characterized in that flame-retardant polymer molding compositions according to 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, lamination or coating at higher temperatures to the flame-retardant polymer molding is processed.
• carbodiimides may be included. Examples
• Polyamide 6.6 PA 6.6 GV: Ultramid ® A27 (BASF AG, Germany.) Polyamide 6T / 66: Zyter HTN FE 8200 (DuPont, USA)
• Polyamide 6T / 6I (amorphous): Grivory ® G21, EMS Grivory, CH
• Polyamide 610 Ultramid ® S, BASF AG, D.
• DEPAL diethylphosphinic acid
• PHOPAL Aluminum salt of phosphorous acid
• Aromatic di- or tri-carboxyl esters or amides (component E):
• Licomont ® CaV 102 (Ca salt of montan wax acid), Fa. Clariant (Germany) GmbH, D
• Injection molding machine (type Arburg 320 C Allrounder) processed to test specimens at melt temperatures of 250 to 300 ° C and based on the UL 94 test
• the flowability of the molding compositions was determined by determining the
• MVR Melt volume index
• V1-V3 are comparative examples, B1 to B3 polyamide molding composition according to the invention
• polyamide 6T / 66 the system DEPAL + MPP can not be used, it is already observed in the compounding strong decomposition. The polymer strand foams up, granulation is not possible.
• polyamide according to the invention with DEPAL, PHOPAL and glass fibers is easy to process and achieves

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• 2013
  • 2013-03-08 DE DE102013004046.9A patent/DE102013004046A1/de not_active Withdrawn
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