WO2000066658A1 - Matieres moulables thermoplastiques - Google Patents

Matieres moulables thermoplastiques Download PDF

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Publication number
WO2000066658A1
WO2000066658A1 PCT/EP2000/003810 EP0003810W WO0066658A1 WO 2000066658 A1 WO2000066658 A1 WO 2000066658A1 EP 0003810 W EP0003810 W EP 0003810W WO 0066658 A1 WO0066658 A1 WO 0066658A1
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weight
radical
acid
independently
alkyl
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PCT/EP2000/003810
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German (de)
English (en)
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Martin Klatt
Michael Nam
Karl Häberle
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Basf Aktiengesellschaft
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Priority to AU45583/00A priority Critical patent/AU4558300A/en
Publication of WO2000066658A1 publication Critical patent/WO2000066658A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/14—Macromolecular materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • 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

Definitions

  • the invention relates to thermoplastic molding compositions containing
  • thermoplastic polymer A) 10 to 99% by weight of at least one thermoplastic polymer
  • R 1 , R 2 independently of one another are hydrogen, Ci to Cio alkyl, C 6 to C ⁇ 2 aryl, C 7 to C ⁇ 3 aralkyl,
  • R3 is a hydrogen, Ci to Cio-alkyl, C ⁇ - to C ⁇ 2 aryl, C 7 - to C 13 aralkyl, C 7 - to C ⁇ 3 alkylaryl radical,
  • R 4 , R i3 independently of one another are NCO or NHCOOR ', where R' is an alkylpolyether glycol or an alcohol having 1 to 20 C atoms,
  • Cio-alkyl C 6 - to C ⁇ 2 -aryl, C 7 - to C i3 aralkyl -, C - to C 13 alkylaryl radical,
  • R 14 , R 15 , R independently of one another a hydrogen residue or
  • R 17 is a hydrogen, Ci to Cio alkyl, C 8 to Ci 2 aryl, C 7 to C 3 aralkyl, C 7 to C 13 alkylaryl radical,
  • Inorganic flame retardants which have to be used in large quantities in order to be effective.
  • Nitrogen-containing FR systems such as melamine cyanurate, which have a limited effectiveness in thermoplastics e.g. Polyamide shows. In reinforced polyamide, it is only effective in combination with shortened glass fibers. Melamine cyanurate alone is not effective in polyesters.
  • JP-A 09/157 503 discloses polyester molding compositions with MC, phosphorus compounds and lubricants which contain less than 10% reinforcing agents. Flame retardant and mechanical properties of such molding compositions are in need of improvement as well as migration and phenol formation during processing.
  • WO 97/05705 discloses combinations of MC with phosphorus-containing compounds and lubricants for polyesters.
  • the present invention was therefore based on the object of providing halogen-free, flame-retardant thermoplastics which show improved stability at high long-term use temperatures and reduce the degradation of the polymer matrix in a dry, warm environment. At the same time, blooming and the tendency of the flame retardants to corrode should be minimized. Accordingly, the molding compositions defined at the outset were found. Preferred embodiments can be found in the subclaims.
  • the molding compositions according to the invention contain 10 to 99, preferably 20 to 95 and in particular 30 to 80% by weight of a thermoplastic polymer.
  • thermoplastics of all kinds.
  • suitable thermoplastics can be found, for example, in the plastic pocket book (ed. Saechtling), edition 1989, where sources of supply are also mentioned. Processes for the production of such thermoplastics are known per se to the person skilled in the art. Some preferred types of plastic are explained in more detail below.
  • polyesters based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.
  • a first group of preferred polyesters are polyalkylene terephthalates with 2 to 10 carbon atoms in the alcohol part.
  • Such polyalkylene terephthalates are known per se and are described in the literature. They contain an aromatic ring in the main chain, which comes from the aromatic dicarboxylic acid.
  • the aromatic ring can also be substituted, e.g. by halogen such as chlorine and bromine or by -CC alkyl groups such as methyl, ethyl, i- or n-propyl and n-, i- or t-butyl groups.
  • polyalkylene terephthalates can be prepared in a manner known per se by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol%, of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid,
  • Sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids can be replaced.
  • aliphatic dihydroxy compounds are diols with 2 to 6 carbon atoms, in particular 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclo - hexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol or mixtures thereof are preferred.
  • polyesters (A) are polyalkylene terephthalates which are derived from alkane diols having 2 to 6 carbon atoms. Of these, polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are preferred in particular. PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight 1,6-hexanediol and / or 5-methyl-1,5-pentanediol as further monomer units are further preferred.
  • the viscosity number of the polyesters (A) is generally in the range from 50 to 220, preferably from 80 to 160 (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (weight ratio 1: 1 at 25 ° C) according to ISO 1628.
  • polyesters whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester.
  • Such polyesters can be produced, for example, by the process of DE-A 44 01 055.
  • the carboxyl end group content is usually determined by titration methods (e.g. potentiometry).
  • Particularly preferred molding compositions contain as component A) a mixture of polyethylene terephthalate (PET) and polyalkylene terephthalates with 3 to 10 carbon atoms in the alcohol part, in particular polybutylene terephthalate (PBT).
  • the proportion of polyethylene terephthalate in the mixture is preferably up to 50, in particular 10 to 30% by weight, based on 100% by weight of A).
  • Such molding compositions according to the invention show very good flame retardant properties and better mechanical properties.
  • PET recyclates also called scrap PET
  • PBT polyalkylene terephthalates
  • Production waste in the case of polycondensation or in processing for example sprues in injection molding processing, start-up goods in injection molding processing or extrusion, or edge sections of extruded sheets or foils.
  • Post consumer recyclate these are plastic items that are collected and processed by the end consumer after use. The most dominant item in terms of quantity are blow-molded PET bottles for mineral water, soft drinks and juices.
  • Both types of recyclate can either be in the form of regrind or in the form of granules. In the latter case, the pipe cyclates are melted and granulated in an extruder after separation and cleaning. This usually facilitates handling, free-flowing properties and meterability for further processing steps.
  • Recycled materials 15 which are both granulated and in the form of regrind can be used, the maximum edge length being 6 mm, preferably less than 5 mm.
  • the residual moisture content after drying is preferably 0.01 to 0.7, in particular 0.2 to 0.6%.
  • Aromatic dicarboxylic acids which are suitable are the compounds already described for the polyalkylene terephthalates. Mixtures of 5 to 100 mol% isophthalic acid and 0 to 30 95 mol% terephthalic acid, in particular mixtures of approximately 80% terephthalic acid with 20% isophthalic acid to approximately equivalent mixtures of these two acids, are used.
  • 2,2-di - (4'-hydroxyphenyl) propane 2,2-di (3 ', 5-dichlorodihydroxyphenyl) ropane, 1,1-di- (4' -hydroxyphenyl) cyc1ohexane, 3,4'-dihydroxybenzophenone, 4 , 4 '-Dihydroxydiphenylsulfone and 2,2 -Di (3', 5 '-dimethyl-4' -hydroxyphenyl) propane
  • mixtures of polyalkylene terephthalates and fully aromatic polyesters can also be used. These generally contain 20 to 98% by weight of the polyalkylene terephthalate and 2 to 80% by weight of the fully aromatic polyester.
  • Polyesters for the purposes of the present invention are also to be understood as meaning polycarbonates which can be obtained by polymerizing aromatic dihydroxy compounds, in particular bis - (4-hydroxyphenyl) 2, 2-propane (bisphenol A) or its derivatives, for example with phosgene. Corresponding products are known and described in the literature and for the most part also available commercially.
  • the amount of the polycarbonates is up to 90% by weight, preferably up to 50% by weight, in particular 10 to 30% by weight, based on 100% by weight of component (A).
  • polyester block copolymers such as copolyether esters can also be used.
  • Products of this type are known per se and are described in the literature, for example in US Pat. No. 3,651,014.
  • Corresponding products are also available on the market, eg Hytrel ® (DuPont).
  • the molecular weight of these known and commercially available polymers is generally in the range from 1,500 to 2,000,000, preferably in the range from 70,000 to 1,000,000.
  • Vinyl aromatic polymers made from styrene, chlorostyrene, ⁇ -methylstyrene and p-methylstyrene are only representative here; In minor proportions (preferably not more than 20, in particular not more than 8% by weight), comonomers such as (meth) acrylonitrile or (meth) acrylic acid esters can also be involved in the structure.
  • Particularly preferred vinyl aromatic polymers are polystyrene and impact modified polystyrene. It is understood that mixtures of these polymers can also be used.
  • the production is preferably carried out according to the method described in EP-A-302 485.
  • Preferred ASA polymers are made up of a soft or rubber phase made of a graft polymer of:
  • a 3 10 to 50 preferably 10 to 45 and in particular 15 to 35% by weight of acrylonitrile and / or methacrylonitrile.
  • the main monomers used for the production of the elastomer are an) esters of acrylic acid with 2 to 10 C atoms, in particular 4 to 8 C atoms.
  • Particularly preferred monomers here are tert.-, iso- and n-butyl acrylate and 2-ethylhexyl acrylate, of which the latter two are particularly preferred.
  • Methods for producing the graft base Ai are known per se and e.g. described in DE-B 1 260 135. Corresponding products are also commercially available.
  • the graft copolymer Ai + A 2 generally has an average particle size of 100 to 1,000 nm, in particular from 200 to 700 nm, (mean weight average).
  • the conditions in the preparation of the elastomer Di) and in the grafting are therefore preferably chosen so that particle sizes result in this range. Measures for this are known and are described, for example, in DE-PS 1 260 135 and DE-OS 28 26 925 as well as in Journal of Applied Polymer Science, Vol. 9 (1965), pp. 2929 to 2938.
  • the particle enlargement of the latex of the elastomer can be accomplished, for example, by means of agglomeration.
  • the products contained as component A 3 can be produced, for example, by the process described in DE-AS 10 01 001 and DE-AS 10 03 436. Such copolymers are also commercially available.
  • the weight average molecular weight determined by light scattering is preferably in the range from 50,000 to 500,000, in particular from 100,000 to 250,000.
  • Suitable SAN polymers as component A) are described above (see A 31 and A 32 ).
  • a 3 1 to 40% by weight of an ASA or ABS polymer or their
  • the preferred partially aromatic copolyamides with a low triamine content can be prepared by the processes described in EP-A 129 195 and 129 196.
  • Polyphenylene ethers in which the substituents are alkyl radicals having 1 to 4 carbon atoms are preferably used.
  • Functionalized or modified polyphenylene ethers are known per se, e.g. from WO-A 86/02086, WO-A 87/00540, EP-A-222 246, EP-A-223 116 and EP-A-254 048 and are preferably used for mixtures with PA or polyester.
  • a 2 0 to 25, preferably 0 to 20% by weight of a vinylaromatic polymer, a 3 ) 0.05 to 5, preferably 0.05 to 2.5% by weight of at least one compound from the group formed from
  • R 6 R 3 where R 1 to R 6 are alkyl groups with 1 to 8 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, aryl groups such as phenyl, naphthyl or 5- or 6-membered heterocycles with a ⁇ -electron system and nitrogen Represent oxygen or sulfur as heteroatoms.
  • the substituents R 1 to R 6 can in turn contain functional groups as substituents, such as carboxyl, carboxyl derivative, hydroxyl, amino, thiol or epoxy groups. Examples are 2,3-dimethyl-2,3-diphenylbutane, 3, 4 -dimethyl-3, 4 -diphenylhexane and 2, 2, 3, 3-tetraphenylbutane.
  • Particularly preferred polyphenylene ethers A) in the molding compositions according to the invention are obtained by modification with maleic acid, maleic anhydride and fumaric acid.
  • Such polyphenylene ethers preferably have an acid number from 1.8 to 3.2, in particular from 2.0 to 3.0.
  • the acid number generally corresponds to the amount of base in mg which is required to neutralize 1 g of an acid-modified polyphenylene ether B) (according to DIN 53 402).
  • thermoplastic polyurethanes TPU
  • TPU thermoplastic polyurethanes
  • Suitable TPUs can be produced, for example, by reacting
  • Suitable organic diisocyanates are, for example, aliphatic, cycloaliphatic and preferably aromatic diisocyanates.
  • aliphatic diisocyanates such as hexamethylene diisocyanate
  • cycloaliphatic diisocyanates such as isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2, 4- and -2,6- cyclohexane diisocyanate and the corresponding isomer mixtures
  • 4,4'-, 2,4'- and 2,2'-dicyclohexylmethane diisocyanate as well as the corresponding isomer mixtures and preferably aromatic diisocyanates
  • 2,4-tolylene diisocyanate mixtures of 2,4- and 2,6-tolylene diisocyanate, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate.
  • Polyetherols and polyesterols are preferably suitable as higher molecular weight polyhydroxyl compounds (b) with molecular weights of 500 to 8000.
  • hydroxyl-containing polymers for example polyacetals, such as polyoxymethylenes and, above all, water-insoluble formals, for example polybutanediol formal and polyhexanediol formal, and polycarbonates, in particular those made from diphenyl carbonate and 1, 6-hexanediol, produced by transesterification, with the above-mentioned molecular weights are also suitable.
  • the polyhydroxyl compounds must be at least predominantly linear, ie they have a difunctional structure in the sense of the isocyanate reaction.
  • Suitable polyetherols can be prepared by reacting one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen atoms bonded.
  • alkylene oxides are: ethylene oxide, 1,2-propylene oxide, 1,2- and 2,3-butylene oxide. Ethylene oxide and mixtures of propylene oxide-1, 2 and ethylene oxide are preferably used.
  • the alkylene oxides can be used individually, alternately in succession or as a mixture.
  • starter molecules examples include water, amino alcohols, such as N-alkyl-diethanolamines, for example N-methyl-diethanolamine, and diols, such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol and 1,6-hexanediol. If appropriate, mixtures of starter molecules can also be used.
  • Suitable polyetherols are also those containing hydroxyl groups
  • Polyetherols of propylene oxide-1,2 and ethylene oxide are preferably used in which more than 50%, preferably 60 to 80% of the OH groups are primary hydroxyl groups and in which at least part of the ethylene oxide is arranged as a terminal block; e.g. in particular polyoxetetramethylene glycols.
  • Such polyetherols can be obtained by e.g. first polymerized to the starter molecule the 1,2-propylene oxide and then the ethylene oxide or first copolymerized all of the 1,2-propylene oxide in a mixture with part of the ethylene oxide and then polymerized the rest of the ethylene oxide or gradually a part of the ethylene oxide, then that all propylene oxide-1, 2 and then the rest of the ethylene oxide, polymerized onto the starter molecule.
  • the essentially linear polyetherols have molecular weights of 500 to 8000, preferably 600 to 6000 and in particular 800 to 3500. They can be used both individually and in the form of mixtures with one another.
  • Suitable polyesterols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms and polyhydric alcohols.
  • suitable dicarboxylic acids are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid, and aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid.
  • the dicarboxylic acids can be used individually or as mixtures, for example in the form of a succinic, glutaric and adipic acid mixture. Mixtures of aromatic and aliphatic dicarboxylic acids can also be used.
  • dicarboxylic acid derivatives such as dicarboxylic acid esters with 1 to 4 carbon atoms in the alcohol radical, dicarboxylic acid anhydrides or dicarboxylic acid chlorides instead of the dicarboxylic acids.
  • polyhydric alcohols are glycols having 2 to 10, preferably 2 to 6, carbon atoms, such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 10, 2-decanediol, 2-dimethylpropanediol-1,3, propanediol-1,3 and dipropylene glycol.
  • the polyhydric alcohols can be used alone or, if appropriate, in mixtures with one another.
  • esters of carbonic acid with the diols mentioned in particular those with 4 to 6 carbon atoms, such as 1,4-butanediol and / or 1,6-hexanediol, condensation products of ⁇ -hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, and preferably polymerization products of Lactones, for example optionally substituted ⁇ -caprolactones.
  • Dialkylene glycol polyadipates with 2 to 6 carbon atoms in the alkylene radical such as, for. B. Ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol-butanediol-1,4-polyadipates, 1,6-hexanediol-neopentyl glycol polyadipates, polycaprolactones and in particular
  • the polyesterols have molecular weights from 500 to 6000, preferably from 800 to 3500.
  • Suitable chain extenders (c) with molecular weights of 60 to 400, preferably 60 to 300, are preferably aliphatic diols with 2 to 12 carbon atoms, preferably with 2, 4 or 6 carbon atoms, such as e.g. Ethanediol, hexanediol-1, 6, diethylene glycol, dipropylene glycol and in particular butanediol-1, 4 into consideration.
  • diesters of terephthalic acid with glycols having 2 to 4 carbon atoms such as e.g. Terephthalic acid bis-ethylene glycol or butanediol-1,4, hydroxyalkylene ether of hydroquinone, e.g. 1,4-di- ( ⁇ -hydroxyethyl) hydroquinone,
  • (cyclo) aliphatic diamines such as, for example, 4,4'-diamino-dicyclohexylmethane, 3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane, Isophorone-diamine, ethylenediamine, 1,2-, 1,3-propylene-diamine, N-methyl-propylenediamine-1,3, N, N'-dimethyl-ethylenediamine and aromatic diamines such as 2,4- and 2, 6-tolylene-diamine, 3, 5-diethyl-2, 4- and -2, 6-toluylene-diamine and primary site-ho-di-, tri- and / or tetraalkyl-substituted 4, 4'-diamino-diphenylmethane.
  • 4,4'-diamino-dicyclohexylmethane 3,3'-dimethyl-4,4'-diamino
  • the structural components (b) and (c) can be varied in relatively wide molar ratios. Molar ratios of polyhydroxyl compounds (b) to chain extenders (c) from 1: 1 to 1:12, in particular from 1: 1.8 to 1: 6.4, have proven successful, the hardness and melting point of the TPU increasing with the content of Diols increases.
  • the structural components (a), (b) and (c) are reacted in the presence of optionally catalysts (d), auxiliaries and / or additives (e) in amounts such that the equivalence ratio of NCO groups of Diisocyanates (a) to the sum of the hydroxyl groups or hydroxyl and amino groups of components (b) and (c) 1: 0.85 to 1.20, preferably 1: 0.95 to 1: 1.05 and in particular 1: 0, Is 98 to 1.02.
  • Suitable catalysts which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the structural components (b) and (c) are the tertiary amines known and customary in the prior art, such as e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane and the like, and in particular organic metal compounds such as titanium acid esters, iron compounds such as e.g. Iron (III) acetyl acetonate, tin compounds, e.g.
  • Triethylamine dimethylcyclohexylamine, N-methylmorpholine, N, N '-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane
  • the catalysts are usually used in amounts of 0.001 to 0.1 part per 100 parts of polyhydroxy compound (b).
  • auxiliary components and / or additives (e) can also be incorporated into the structural components (a) to (c).
  • examples include lubricants, inhibitors, stabilizers against hydrolysis, light, heat or discoloration, dyes, pigments, inorganic and / or organic fillers and plasticizers. rather, as well as additives for the production of foamed TPU moldings.
  • the molding compositions according to the invention contain 1 to 50, preferably 5 to 30 and in particular 5 to 20% by weight of a mixture of
  • R 1 , R 2 independently of one another are a hydrogen, Ci to Cio alkyl, C 6 to C 2 aryl, C 7 to C13 aralkyl, C 7 to C13 alkylaryl radical,
  • R 3 is a hydrogen f -, Ci - to Cio alkyl, C ⁇ to Ci 2 aryl, C 7 to C i3 aralkyl, C 7 to C 13 alkyl aryl radical,
  • R 4 , R 13 independently of one another are NCO or NHCOOR ', where R' is an alkyl polyether glycol or an alcohol having 1 to 20 C atoms,
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 independently of one another are hydrogen, C - to Cio-alkyl, C 6 - to C ⁇ 2 -aryl-, C 7 - to C 13 aralkyl, C 7 to C 13 alkylaryl,
  • Rl, R15, R16 independently of one another a hydrogen residue or
  • R 1 and R 2 each independently of one another preferably represent Ci to Cio, particularly preferably Ci to C - and moreover preferably C 3 alkyl. Of these, a 2 -propyl radical is particularly preferred.
  • C 6 - to C ⁇ aryl radicals according to the invention are C ß - to Cio-aryl and preferably C ⁇ - to Cs aryl group is particularly preferred.
  • aryl groups phenyl and naphthyl groups are particularly preferred.
  • Preferred aralkyl radicals with preferably 7 to 14 carbon atoms are toluene, xylyl, tert. -Butyl-phenyl and di -tert. -butyl-phenyl.
  • Benzyl is preferred as the alkylaryl radical having preferably 7 to 14 carbon atoms.
  • variables c and d independently of one another are preferably 0, 1, 2, 3, 4 or 5 and particularly preferably 0, 1 or 2. Furthermore, it is preferred if c and d are each 0.
  • R 1 and R 2 For the preferred meanings of R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 , the explanations given for R 1 and R 2 apply, with the difference that instead of the 2-propyl radical, one is used here Methyl radical is particularly preferred.
  • radicals R 14 , R 15 and R 16 are not a hydrogen atom.
  • Triphenylphosphine oxide, tricyclohexylphosphine oxide and tris (n-octyl) phosphine oxide are particularly preferably used.
  • Also suitable as a phosphorus compound is triphenylphosphine sulfide and its derivatives of the phosphine oxides and triphenylphosphate as described above.
  • Phosphorus compounds of valence level ⁇ 0 is the elementary phosphorus. Red and black phosphorus are possible. Red phosphorus is preferred.
  • Phosphorus compounds of the "oxidation level" +1 are e.g. Hypophosphites.
  • examples are organic hypophosphites, such as
  • Cellulose hypophosphite esters esters of hypophosphorous acids with diols, e.g. of 1, 10-dodecyldiol.
  • Substituted phosphinic acids and their anhydrides e.g. Diphenylphosphinic acid can be used.
  • dipotolylphosphinic acid dicresylphosphinic anhydride.
  • hydroquinone ethylene glycol
  • Aryl (alkyl) phosphinamides such as e.g.
  • Aralkylene e.g. Pheny1-methylene, phenylethylene, phenylpropylene, phenylbutylene;
  • M is an alkaline earth metal, alkali metal, Al, Zn, Fe, boron, Ti, Zr;
  • Phosphorus compounds of oxidation level +3 are derived from the phosphorous acid.
  • Cyclic phosphonates derived from pentaerythritol, neopentyl glycol or catechol are suitable, as in general formula VIII
  • Hypodiphosphates such as e.g. Tetraphenyl hypodiphosphate or bisneopentyl hypodiphosphate.
  • Alkyl and aryl-substituted phosphates are particularly suitable as phosphorus compounds of oxidation level +5.
  • Examples are phenylbisdodecylphosphate, phenylethyl hydrogen phosphate, phenyl bis (3,5,5-trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di (tolyl) phosphate, diphenyl hydrogen phosphate, bis (2-ethylhexyl) -p-tolyl phosphate, tritolyl phosphate -ethyl-hexy1) -phenyl phosphate, di (nony1) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) -p-tolyl phosphate, p-tolyl bis (2, 5, 5-trimethylhexyl) phosphate or 2-ethylhexyldiphenyl
  • Phosphorus compounds in which each radical is an aryloxy radical are particularly suitable.
  • Triphenyl phosphate and resorcinol bis - (diphenyl phosphate) (RDP) and its core-substituted derivatives of the general formula IX are very particularly suitable
  • R 21 to R 24 are an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical, which can be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl,
  • R 25 is a divalent phenol radical, preferred
  • q is an average value between 0.1 and 100, preferably 0.5 to 50, in particular 0.8 to 10 and very particularly 1 to 5.
  • the phosphorus compound of the general formula X is particularly preferred
  • R 2 ⁇ , R 7, R 28 R 29 independently of one another hydrogen atom, Ci to C 6 alkyl,
  • r, s, t, u independently of one another 1, 2, 3, 4 or 5, 1 and the para position of the corresponding radical to the phosphorus being preferred.
  • RDP The commercially available RDP products under the trademarks Fyroflex®-RDP (Akzo Nobel) and CR 733 -S (Daihachi) are due to the manufacturing process mixtures of approx. 85% RDP with approx. 2.5% triphenyl phosphate and approx. 12.5% oligomeric proportions in which the degree of oligomerization is usually less than 10. Cyclic phosphates can also be used as phosphorus compounds. Diphenylpentaerythritol diphosphate and phenylneopentyl phosphate are particularly suitable.
  • Such polymeric, preferably halogen-free, organic phosphorus compounds with phosphorus in the polymer chain arise, for example, in the production of pentacyclic, unsaturated phosphorine dihalides, as described, for example, in DE-A 2036173.
  • the molecular weight measured by vapor pressure osmometry in dimethylformamide, the polyphospholine oxides should be in the range from 500 to 7,000, preferably in the range from 700 to 2,000.
  • the phosphorus has the oxidation state -1.
  • inorganic coordination polymers of aryl (alkyl) phosphinic acids such as e.g. Poly-b-sodium (I) methylphenylphosphinate can be used as phosphorus compounds. Their manufacture is specified in DE-A 3140520. The phosphorus has an oxidation number of +1.
  • polymeric phosphorus compounds can be obtained by the reaction of a phosphonic acid chloride, such as e.g. Phenyl, methyl, propyl, styryl and vinyl phosphonic acid dichloride with bifunctional phenols, such as e.g. Hydroquinone, resorcinol, 2, 3, 5-trimethylhydroquinone, bisphenol-, tetramethylbisphenol-A arise.
  • a phosphonic acid chloride such as e.g. Phenyl, methyl, propyl, styryl and vinyl phosphonic acid dichloride
  • bifunctional phenols such as e.g. Hydroquinone, resorcinol, 2, 3, 5-trimethylhydroquinone, bisphenol-, tetramethylbisphenol-A arise.
  • polymeric phosphorus compounds which may be present in the molding compositions according to the invention are prepared by reacting phosphorus oxide trichloride or phosphoric acid ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and other hydroxyl-bearing compounds (cf. Houben-Weyl -Müller, Thieme- Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)).
  • Polymeric phosphonates can also be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (cf. DE-A 2925208) or by reactions of phosphonic acid esters with diamines or diamines or hydrazides (cf. US Pat. No.
  • the inorganic poly (ammonium phosphate) can also be used. It is also possible to use oligomeric pentaerythritol phosphites, phosphates and phosphonates according to EP-B 8486, for example Mobil Antiblazeä 19 (registered trademark of Mobil Oil) as phosphorus compounds.
  • a component B) according to the invention is preferred which over a period of 1 to 100, preferably 2 to 50 and particularly preferably 10 to 30 days from the time when the phosphorus compound is brought into contact with the stabilizer compound by a maximum of 20, preferably a maximum of 15 and particularly preferably at most 5% deviates from the acid number at the time of contact.
  • the phosphorus compound and the stabilizer compound and, if appropriate, other auxiliaries and additives which are usually to be added to them can be brought into contact with one another by all processes which are generally known to the person skilled in the art. However, mixing in tanks with moving mixers or mixing the composition, which is moved, for example, through a downpipe, using a static mixer has proven successful.
  • composition of component B according to the invention is preferably used to increase the storage stability or to reduce the tendency to metal corrosion of phosphorus compounds.
  • the storage stability is usually determined via the deviation of the acid number over the storage period of the corresponding composition.
  • the acid number deviates from the acid number at the beginning of the aforementioned period over a period of 5 days, preferably 2 weeks and particularly preferably one month by at most 10, preferably at most 5 and particularly preferably at most 1%.
  • the strength of the tendency to metal corrosion results from the comparison of the before corrosion of a corresponding connection with or without a stabilizer connection under otherwise identical conditions over a same period of time.
  • Particularly preferred stabilizer compounds contain at least one of the following compounds represented by their structural formulas: Stabaxol® 1 (Rhein Chemie GmbH) Stabaxol® p (Rhein Chemie GmbH)
  • n 1 to 100
  • thermoplastic molding compositions according to the invention can contain 0 to 40, preferably 1 to 30, preferably 1 to 20, and in particular 5 to 15% by weight of a flame retardant, different from bi).
  • Preferred flame retardants are for the combination with b 2 ), in particular nitrogen compounds.
  • the melamine cyanurate which is preferably suitable according to the invention (component C) is a reaction product of preferably equimolar amounts of melamine (formula XI) and cyanuric acid or isocyanuric acid (formulas XIa and Xlb)
  • the commercially available product is a white powder with an average grain size dso of 1.5-7 ⁇ m.
  • melamine borate oxalate and phosphate prim.
  • oxalate and phosphate prim. -phosphate sec. and -pyrophosphate sec.
  • neopentylglycol boric acid melamine and polymeric melamine phosphate CAS No. 56386-64-2).
  • Suitable guanidine salts are CAS number
  • both e.g. Benzoguanamine itself and its adducts or salts as well as the nitrogen-substituted derivatives and its adducts or salts are to be understood.
  • R, R ' have the meaning given in formula XIII and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid and glycolurils of the formula XV or its salts with the above. Acids
  • Suitable products are commercially available or in accordance with DE-A 196 14 424.
  • the aliphatic amines can be 1- to 3-valent. Examples include stearylamine, ethylene diamine, propylene diamine, hexamethylene diamine, di (6-aminohexyl) amine, with ethylene diamine and hexamethylene diamine being particularly preferred.
  • Preferred esters or amides are correspondingly glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • Mixtures of different esters or amides or esters with amides can also be used in combination, the mixing ratio being arbitrary.
  • EPM or EPDM rubbers can preferably also be grafted with reactive carboxylic acids or their derivatives.
  • reactive carboxylic acids or their derivatives e.g. Acrylic acid, methacrylic acid and their derivatives, e.g. Glycidyl (meth) acrylate, as well as maleic anhydride.
  • Copolymers are particularly preferred
  • n-butyl acrylate 1 to 45, in particular 10 to 40% by weight of n-butyl acrylate and / or 2-ethylhexyl acrylate.
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • the ethylene copolymers described above can be prepared by processes known per se, preferably by random copolymerization under high pressure and elevated temperature. Appropriate methods are generally known.
  • Preferred elastomers are also emulsion polymers, the production of which e.g. is described in Blackley in the monograph "Emulsion Polymerization".
  • the emulsifiers and catalysts that can be used are known per se.
  • acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers for the production of the rubber part of the elastomers acrylates such as n-Butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylates, butadiene and isoprene and mixtures thereof.
  • monomers can be combined with other monomers such as e.g. Styrene, acrylonitrile, vinyl ethers and other acrylates or methacrylates such as methyl methacrylate, methyl acrylate, ethyl acrylate and propyl acrylate can be copolymerized.
  • the soft or rubber phase (with a glass transition temperature below 0 ° C) of the elastomers can be the core, the outer shell or a middle shell (in the case of elastomers with more than two layers). in the case of multi-layer elastomers, several shells can also consist of a rubber phase.
  • one or more hard components are involved in the construction of the elastomer, these are generally replaced by Polymerization of styrene, acrylonitrile, methacrylonitrile, ⁇ -methylstyrene, p-methylstyrene, acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
  • styrene acrylonitrile
  • methacrylonitrile ⁇ -methylstyrene
  • p-methylstyrene acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate
  • acrylic acid esters and methacrylic acid esters such as methyl acrylate, ethyl acrylate and methyl methacrylate as the main monomers.
  • further comonomers can also be used here.
  • R 11 is hydrogen, a C 1 -C 4 -alkyl group or an aryl group, in particular phenyl,
  • R 12 is hydrogen, a C ⁇ ⁇ to Cio-alkyl, C 6 - to C ⁇ group 2 -aryl or -OR 13
  • R 13 is a C 1 -C 6 -alkyl or C 1 -C 2 aryl group, which may optionally be substituted with 0 or N-containing groups,
  • X is a chemical bond, a C ⁇ to C ⁇ ⁇ alkylene or C - Ci 2 ⁇ arylene group or
  • Z is a Ci to Cio alkylene or ⁇ to C ⁇ 2 arylene group.
  • the graft monomers described in EP-A 208 187 are also suitable for introducing reactive groups on the surface.
  • acrylamide, methacrylamide and substituted esters of acrylic acid or methacrylic acid such as (Nt-butylamino) ethyl methacrylate, (N, N-dimethylamino) ethyl acrylate, (N, N-dimethylamino) methyl acrylate and (N, N-diethylamino) called ethyl acrylate.
  • the particles of the rubber phase can also be crosslinked.
  • Monomers acting as crosslinkers are, for example, buta-1,3-diene, divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl acrylate, and the compounds described in EP-A 50 265.
  • So-called graft-linking monomers can also be used, i.e. Monomers with two or more polymerizable double bonds, which react at different rates during the polymerization.
  • Compounds are preferably used in which at least one reactive group polymerizes at about the same rate as the other monomers, while the other reactive group (or reactive groups) e.g. polymerizes much slower (polymerize).
  • the different polymerization rates result in a certain proportion of unsaturated double bonds in the rubber. If a further phase is subsequently grafted onto such a rubber, the double bonds present in the rubber react at least partially with the graft monomers to form chemical bonds, i.e. the grafted phase is at least partially linked to the graft base via chemical bonds.
  • graft-crosslinking monomers are monomers containing allyl groups, in particular allyl esters of ethylenically unsaturated carboxylic acids such as allyl acrylate, allyl methacrylate,
  • graft polymers with a core and at least one outer shell have the following structure:
  • graft polymers with a multi-layer structure instead of graft polymers with a multi-layer structure, homogeneous, i.e. single-shell elastomers of buta-l, 3-diene, isoprene and n-butyl acrylate or their copolymers are used. These products can also be prepared by using crosslinking monomers or monomers with reactive groups.
  • emulsion polymers examples include n-butyl acrylate / (meth) acrylic acid copolymers, n-butyl acrylate / glycidyl acrylate or n-butyl acrylate / glycidyl methacrylate copolymers, graft polymers with an inner core of n-butyl acrylate or based on a butadiene and an outer shell from the above mentioned copolymers and copolymers of ethylene with comonomers which provide reactive groups.
  • the elastomers described can also be produced by other customary processes, for example by suspension polymerization. Silicone rubbers as described in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319 290 are also preferred.
  • Fibrous or particulate fillers are carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar, which are present in quantities of up to 50% by weight. %, in particular 1 to 40%, in particular 20 to 35% by weight, are used.
  • Carbon fibers, aramid fibers and potassium titanate fibers may be mentioned as preferred fibrous fillers, with glass fibers being particularly preferred as E-glass. These can be used as rovings or cut glass in the commercially available forms.
  • the fibrous fillers can be surface-pretreated with a silane compound for better compatibility with the thermoplastic.
  • Suitable silane compounds are those of the general formula
  • n is an integer from 2 to 10, preferably 3 to 4 m is an integer from 1 to 5, preferably 1 to 2 k is an integer from 1 to 3, preferably 1
  • Preferred silane compounds are aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl group as substituent X.
  • the silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1.5 and in particular 0.8 to 1% by weight (based on D) for surface coating.
  • Acicular mineral fillers are also suitable.
  • acicular mineral fillers are understood to be mineral fillers with a pronounced acicular character.
  • An example is needle-shaped wollastonite.
  • the mineral preferably has an L / D (length diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 11: 1.
  • the mineral filler can optionally have been pretreated with the abovementioned silane compounds; however, pretreatment is not essential.
  • Kaolin, calcined kaolin, wollastonite, talc and chalk may be mentioned as further fillers.
  • thermoplastic molding compositions according to the invention can contain customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • customary processing aids such as stabilizers, oxidation retardants, agents against heat decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • oxidation retarders and heat stabilizers are sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and their mixtures in concentrations of up to 1% by weight, based on the weight of the thermoplastic molding compositions called.
  • UV stabilizers generally in amounts up to 50%
  • Inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, organic pigments such as phthalocyanines, quinacridones, perylenes and dyes such as nigrosine and anthraquinones can also be added as colorants.
  • Sodium phenylphosphinate, aluminum oxide, silicon dioxide and preferably talc can be used as nucleating agents.
  • Further lubricants and mold release agents which are usually used in amounts of up to 1% by weight, are preferably long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain , saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms) and low molecular weight polyethylene or polypropylene waxes.
  • long-chain fatty acids eg stearic acid or behenic acid
  • their salts eg Ca or Zn stearate
  • montan waxes mixturetures of straight-chain , saturated carboxylic acids with chain lengths of 28 to 32 carbon atoms
  • low molecular weight polyethylene or polypropylene waxes low molecular weight polyethylene or polypropylene waxes.
  • plasticizers are phthalic acid dioctyl ester, phthalic acid dibenzyl ester, phthalic acid butyl benzyl ester, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.
  • the molding compositions according to the invention can also contain 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76% by weight, preferably 70 to 76% by weight.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoropropylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
  • fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size dso (number average) in the range from 0.05 to 10 ⁇ m, in particular from 0.1 to 5 ⁇ m. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which the starting components are mixed in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After the extrusion, the extrudate can be cooled and crushed. Individual components can also be premixed and the remaining starting materials added individually and / or likewise mixed.
  • the mixing temperatures are usually 230 to 290 ° C.
  • components B) to D) can be mixed, made up and granulated with a polyester prepolymer or polyamide prepolymer.
  • the granules obtained are then condensed in the solid phase under inert gas continuously or batchwise at a temperature below the melting point of component A) to the desired viscosity.
  • the thermoplastic molding compositions according to the invention are notable for good mechanical properties and good flame retardant properties. Processing is largely carried out without changing the polymer matrix and the mold coating and metal corrosion tendency are greatly reduced.
  • moldings of this type show improved stability against dry heat or heat. They are suitable for the production of fibers, foils and moldings, in particular for applications in the electrical and electronics sector. These applications include, in particular, lamp parts such as lamp sockets and holders, plugs and connector strips, coil formers, housings for capacitors or contactors, as well as fuse switches, relay housings and reflectors.
  • VZ Viscosity number
  • Component A / 2 polyethylene terephthalate with a VN of 97 ml / g
  • Component bi resorcinol -bis - (diphenylphosphate) (CR 733 -S from Daihachi)
  • n 1 to 100
  • Component b 26 Vestanat® 1890/100 (Hüls AG)
  • Component D / 2 1 1 mixture of Irgafos® 168 and pentaerithritol - tyl - tetrakis - (3 - (3, 5-di - tert.-butyl - -hydroxyphenyl) propionate (Irganox® 1010) (Ciba Speziali tucimie AG)
  • the test of the stability at elevated operating temperatures was carried out as follows: molded parts (small plates 60x60x2 mm, approx. 11 g) were injected. One molded part each was weighed on the analytical balance and heated to the specified temperature in an aluminum pan in a convection oven.
  • Granules were also stored under the above conditions (0/10/20 days at 130 ° C) and the VZ was determined in accordance with ISO 1628.
  • Cu corrosion storage of a copper plate in direct contact with granulate and visual assessment of the formation of deposits.

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Abstract

L'invention concerne des matières moulables thermoplastiques qui contiennent: A) 10 à 99 % en poids d'au moins un polymère thermoplastique; B) 1 à 50 % d'un mélange constitué b1) d'au moins un composé de phosphore et b2) d'au moins un composé stabilisateur correspondant aux formules générales (I) à (IV). Dans la formule (I), R<1>, R<2> représentent, indépendamment l'un de l'autre, un reste hydrogène, alkyle C1-C10, aryle C6-C12, aralkyle C7-C13, alkylaryle C7-C13, a et b valent, indépendamment l'un de l'autre, 1 à 5, et c et d valent, indépendamment l'un de l'autre, 0 à 10. Dans la formule (II), R<3> représente un reste hydrogène, alkyle C1-C<10>, aryle C6-C12, aralkyle C7-C13, alkylaryle C7-C13, e vaut 1 à 4 et f vaut 1 à 100. Dans la formule (III), R<4> et R<13> représentent, indépendamment l'un de l'autre, NCO ou NHCOOR', où R' représente un alkylpolyétherglycol ou un alcool possédant 1 à 20 atomes de C, R<5>, R<6>, R<7>, R<8>, R<9>, R<10>, R<11> et R<12> représentent, indépendamment l'un de l'autre, un reste hydrogène, alkyle C1-C10, aryle C6-C12, aralkyle C7-C13, alkylaryle C7-C13, g vaut 0 à 5 et h vaut 1 à 100. Dans la formule (IV), R<14>, R<15>, R<16> représentent, indépendamment l'un de l'autre, un reste hydrogène ou bien un reste (a), où R<17> représente un reste hydrogène, alkyle C1-C10, aryle C6-C12, aralkyle C7-C13, alkylaryle C7-C13, ou bien (CH2)l-N=C=O, où l vaut 1 à 20, et i vaut 2 à 8, j vaut 1 à i - k, k valant 0 à i - j, ou bien au moins deux de ces groupes. Lesdites matières contiennent également: c) 0 à 40 % en poids d'un agent ignifuge, différent de b1); et D) 0 à 70 % en poids d'autres additifs. La somme des pourcentages en poids des composants A) à D) correspond toujours à 100 %.
PCT/EP2000/003810 1999-05-04 2000-04-27 Matieres moulables thermoplastiques WO2000066658A1 (fr)

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US6964746B2 (en) 2002-06-14 2005-11-15 Clariant Gmbh Mixture of a phosphonite with other components
EP1454948A2 (fr) * 2003-03-03 2004-09-08 Clariant GmbH Combinaison d'agent ignifugeant et stabilisant pour polymères thermoplastiques
EP1454948A3 (fr) * 2003-03-03 2005-02-02 Clariant GmbH Combinaison d'agent ignifugeant et stabilisant pour polymères thermoplastiques
US7255814B2 (en) 2003-03-03 2007-08-14 Clariant Produkte (Deutschland) Gmbh Flame retardant and stabilizer combined for thermoplastics polymers
EP1500676A2 (fr) * 2003-07-14 2005-01-26 Clariant GmbH Polyamide ignifugé
EP1500676A3 (fr) * 2003-07-14 2005-12-14 Clariant GmbH Polyamide ignifugé
US20150175776A1 (en) * 2012-06-05 2015-06-25 Rhein Chemie Rheinau Gmbh Method for stabilizing polymers containing ester groups
JP2017513965A (ja) * 2014-03-04 2017-06-01 エフアールエックス ポリマーズ、インク． エポキシ組成物

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